WO2009084195A1 - ポルフィラジン色素及びこれを含有するインク組成物 - Google Patents
ポルフィラジン色素及びこれを含有するインク組成物 Download PDFInfo
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- WO2009084195A1 WO2009084195A1 PCT/JP2008/003947 JP2008003947W WO2009084195A1 WO 2009084195 A1 WO2009084195 A1 WO 2009084195A1 JP 2008003947 W JP2008003947 W JP 2008003947W WO 2009084195 A1 WO2009084195 A1 WO 2009084195A1
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- 0 CC(C)(*)C(C)(C)C(C)(C)S(N)(=O)=O Chemical compound CC(C)(*)C(C)(C)C(C)(C)S(N)(=O)=O 0.000 description 3
- MXVIJZJDKGHSSJ-UHFFFAOYSA-N CCCNc1nc(Nc2cc(C(O)=O)cc(C(O)=O)c2)nc(Nc2cc(C(O)=O)cc(C(O)=O)c2)n1 Chemical compound CCCNc1nc(Nc2cc(C(O)=O)cc(C(O)=O)c2)nc(Nc2cc(C(O)=O)cc(C(O)=O)c2)n1 MXVIJZJDKGHSSJ-UHFFFAOYSA-N 0.000 description 1
- FFWWXUJRMBNUPJ-UHFFFAOYSA-N CCCNc1nc(Nc2cc(S(O)(=O)=O)ccc2)nc(Nc2cc(S(O)(=O)=O)ccc2)n1 Chemical compound CCCNc1nc(Nc2cc(S(O)(=O)=O)ccc2)nc(Nc2cc(S(O)(=O)=O)ccc2)n1 FFWWXUJRMBNUPJ-UHFFFAOYSA-N 0.000 description 1
- KBOVMICBPFRKLB-UHFFFAOYSA-N NCCNc1nc(Nc(cc2)ccc2C(O)=O)nc(Nc(cc2)ccc2C(O)=O)n1 Chemical compound NCCNc1nc(Nc(cc2)ccc2C(O)=O)nc(Nc(cc2)ccc2C(O)=O)n1 KBOVMICBPFRKLB-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed systems contains four or more hetero rings
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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
- C09B47/08—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex
- C09B47/24—Obtaining compounds having —COOH or —SO3H radicals, or derivatives thereof, directly bound to the phthalocyanine radical
- C09B47/26—Amide radicals
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/0023—Digital printing methods characterised by the inks used
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
Definitions
- the present invention relates to a water-soluble porphyrazine coloring matter or a salt thereof, an ink composition containing the same, and a colored body colored with the same.
- ink ejection methods have been developed in a recording method using an ink jet printer, which is one of the representative methods.
- ink droplets are generated and recorded on various recording materials (paper, film, fabric, etc.).
- This method has been rapidly spreading in recent years due to the features that the recording head and the recording material are not in direct contact, so there is no sound generation and it is quiet, and the size, speed and color are easy. Large growth is expected in the future.
- inks such as fountain pens and felt pens and inks for ink jet recording, inks obtained by dissolving a water-soluble dye in an aqueous medium are used.
- a water-soluble organic solvent is generally added to prevent clogging of the ink at the pen tip or the ink discharge nozzle.
- These inks provide a recording image with sufficient density, do not cause clogging of the pen tip and nozzles, have good drying properties on the recording material, have little bleeding, and have excellent storage stability. Is required.
- a fastness such as water resistance, moisture resistance, light resistance, and gas resistance is required for a recorded image formed by the ink.
- Ink jet nozzle clogging occurs when the water content in the ink evaporates near other nozzles and other solvents and additives, and the pigment solidifies and precipitates when the composition state is low in water and high in solvents and additives. There are many things that come from doing. Therefore, one of the very important required performances is that solids are difficult to deposit even when the ink is concentrated due to evaporation of moisture in the ink. For this reason, high solubility in solvents and additives is one of the properties required for pigments.
- each dye used in the ink especially Y
- each of M and C has a hue close to a standard and is clear.
- the ink is required to be stable against long-term storage, to have a high density of the printed image as described above, and to be excellent in fastness of the printed image.
- inkjet printers Due to recent developments in inkjet technology, the speed of printing in inkjet printing has been dramatically improved. For this reason, there is a movement to use an inkjet printer in the same manner as a laser printer using electronic toner for printing a document on plain paper, which is the main use in an office environment. Inkjet printers have the advantage that the type of recording paper is not limited, and the price of the machine is relatively low. In particular, it is spreading in small to medium-sized office environments such as SOHO. Thus, when an inkjet printer is used for printing on plain paper, hue and water resistance tend to be more important among the quality required for printed matter. In order to satisfy these performances, a method of using a pigment ink has been proposed.
- the pigment ink is not a solution but a dispersion in which a solid pigment is dispersed
- problems such as poor storage stability of the ink when the pigment ink is used, problems such as clogging of the nozzles of the printer head, etc. Is more likely to occur compared to dye inks.
- pigment ink it is often a problem that the printed image has low abrasion resistance.
- dye inks since the dye which is a pigment component is dissolved in the ink, problems caused by such a pigment ink are relatively unlikely to occur.
- dye inks are generally significantly inferior to pigment inks especially in terms of water resistance, their improvement is strongly desired.
- Typical examples of water-soluble cyan dyes used in inks suitable for inkjet recording are phthalocyanine dyes and triphenylmethane dyes.
- Typical phthalocyanine dyes reported and used most widely include phthalocyanine derivatives classified as A to H below.
- Phthalocyanine dyes described in Patent Documents 8, 9, and 12, etc. A phthalocyanine compound in which the substitution position of the substituent is controlled, a phthalocyanine dye having a substituent introduced at the ⁇ -position].
- the benzopyridoporphyrazine-based dyes having a nitrogen-containing heterocycle and a benzene ring disclosed in Patent Documents 10, 13, 14, and 15 are provided with active gas resistance, light resistance, moisture resistance, hue, and the like. There is no mention of improving the water resistance of plain paper.
- the present invention has high solubility in water or a water-soluble organic solvent, has a hue and sharpness suitable for ink jet recording, has a high color density, and has light resistance, gas resistance, moisture resistance, water resistance, etc. It is an object of the present invention to provide a water-soluble cyan dye excellent in water fastness, particularly in various plain papers, and an ink composition having good storage stability containing the same.
- rings A, B, C and D represented by broken lines each independently represent an aromatic 6-membered ring, and among the four rings A to D, the average value is at least 1.0.
- benzene rings, and at least 0.5 of them are nitrogen-containing heteroaromatic rings
- E represents an alkylene group
- X and Y are each independently an anilino group having 1 to 3 carboxy groups; All are average values, b is 0 to 3.4, c is 0.1 to 3.5, and the sum of b and c is 1.0 to 3.5.
- rings A, B, C and D represented by broken lines have the same meaning as described in (1) above, and n is an average value of 1.0 to 3.5. ]
- a ring-shaped pyridine ring, and 1.0 to 3.5 of the rest are benzene rings, E is C2-C4 alkylene;
- X and Y are each independently an anilino group having 1 to 3 carboxy groups; All are average values, b is 0 to 3.4, c is 0.1 to 3.5, and the sum of b and c is 1.0 to 3.5.
- Porphyrazine dye or a salt thereof, (7) Porphyrazine coloring matter or salt thereof according to the above (1) or (2) represented by the following formula (2)
- Z 1 to Z 8 each independently represent a nitrogen atom or a carbon atom, and four of Z 1 and Z 2 , Z 3 and Z 4 , Z 5 and Z 6, and Z 7 and Z 8 Among the combinations, at least 1.0 on average is a combination of carbon atoms, and among the remaining, at least 0.5 is a combination of nitrogen atoms and carbon atoms or a combination of nitrogen atoms, E, X, Y, b, and c represent the same meaning as described in (1) above. ].
- Z 1 to Z 8 represent the same meaning as described in (7) above, and n is an average value of 1.0 to 3.5. ]
- the water-soluble porphyrazine coloring matter or salt thereof represented by the above formula (1) of the present invention is excellent in solubility in water or a water-soluble organic solvent. Further, it has a feature of good filterability, for example, for a membrane filter in the process of producing an ink composition, and gives a very clear cyan hue on an ink jet recording paper.
- the ink composition of the present invention containing this compound has very good storage stability without solid precipitation, changes in physical properties, hue changes and the like after long-term storage.
- a printed matter using the ink composition of the present invention as an ink for ink jet recording has an ideal hue as a cyan hue without selecting a recording material (for example, paper, film, etc.), and a photographic color image Can be reproduced faithfully on paper.
- the ink composition of the present invention has extremely improved water resistance on plain paper compared to conventional dye inks.
- a recording material coated with a porous white inorganic material on the surface such as a paper for exclusive use for inkjet for photographic image quality or a film
- various fastness properties that is, water resistance, moisture resistance, gas resistance Property and light resistance are good. Therefore, the long-term storage stability of photographic-tone recorded images is also excellent.
- the ink composition is very suitable for ink jet printing, which is one of the characteristics that a recording medium is not selected.
- the water-soluble porphyrazine coloring matter represented by the above formula (1) is extremely useful as a cyan coloring matter for inks, particularly inks for inkjet recording.
- the porphyrazine dye or a salt thereof of the present invention is represented by the formula (1) or the formula (2), and is substantially a mixture of the porphyrazine dye or a salt thereof.
- the “porphyrazine dye or a salt thereof” of the present invention will be simply referred to as “porphyrazine dye” hereinafter for convenience.
- the superscript "RTM” indicates a registered trademark.
- the rings A, B, C and D represented by broken lines each independently represent an aromatic 6-membered ring (hereinafter also referred to as an aromatic 6-membered ring),
- an aromatic 6-membered ring In each of the rings A to D, at least 1.0 in average is a benzene ring, and at least 0.5 is a nitrogen-containing heteroaromatic ring.
- the number of benzene rings or nitrogen-containing heteroaromatic rings in rings A to D is represented by an average value of the number of benzene rings or nitrogen-containing heteroaromatic rings in the dye represented by the formula (1).
- the average is 2 of all dye molecules.
- One-half is a compound in which all of A to D are benzene rings, and the remaining half is a compound in which one of A to D is a nitrogen-containing heteroaromatic ring.
- the dye represented by the formula (1) in which one is a benzene ring and 1.5 is a nitrogen-containing heteroaromatic ring, on average, one-half of all dye molecules are A to D, and two are It is a benzene ring compound, and the remaining half is that one of A to D is a nitrogen-containing heteroaromatic ring compound. Therefore, when the number of nitrogen-containing heteroaromatic rings is 1 or less, the dye represented by the formula (1) includes a dye in which at least one of rings A to D is the nitrogen-containing heteroaromatic ring, Each of A to D includes both of the dyes each having a benzene ring.
- the porphyrazine coloring matter of the present invention is not usually a simple mixture of the two components as described above, but the above value is an average value of the mixture.
- the nitrogen-containing heteroaromatic ring is preferably a nitrogen-containing heteroaromatic 6-membered ring containing 1 to 2 nitrogen atoms, and examples thereof include a pyridine ring, a pyrazine ring, a pyrimidine ring, and a pyridazine ring.
- a pyridine ring or a pyrazine ring is preferable, and a pyridine ring is more preferable.
- the preferred specific number of nitrogen-containing heteroaromatic rings is usually 0.5 to 3.0 on average, preferably 0.5 to 2 on average. .5, more preferably 0.5 to 2.0, and the remainder is a benzene ring. That is, the specific number of benzene rings in this case is usually 1.0 to 3.5 on average, preferably 1.5 to 3.5, more preferably 2.0 to 3.5. It is a piece. When two or more consecutive carbon atoms are present, the nitrogen-containing heteroaromatic ring may be condensed at any position.
- the 2-position and 3-position or the 3-position and 4-position may be mentioned, and it is preferable that the ring is condensed at the 2-position and 3-position.
- they are the 2nd and 3rd positions.
- the number of nitrogen-containing heteroaromatic rings may be appropriately adjusted in consideration of water resistance and solubility, and a balanced ratio may be selected.
- the number of nitrogen-containing heteroaromatic rings is an average value, and it is preferable when the number is within the above range among the four rings A, B, C and D.
- the average number of aromatic rings may be 0.50 to 2.0, or 0.50 to 1.5, and in some cases 0.70 to 1.5. In this case, the remainder is a benzene ring.
- E represents an alkylene group.
- the alkylene group may be linear, branched or cyclic, but is preferably linear or cyclic, more preferably linear.
- the number of carbon atoms is usually 2 to 12, preferably 2 to 6, and more preferably 2 to 4.
- Specific examples include linear groups such as ethylene group, propylene group, butylene group, pentylene group and hexylene group; cyclopropylene diyl, 1,2- or 1,3-cyclopentylenediyl, 1,2-, 1 , 3- or 1,4-cyclohexylenediyl and the like; and the like.
- a preferable group for E is a C2-C4 alkylene group, more preferably an ethylene group, a propylene group and a butylene group, and still more preferably an ethylene group or a propylene group.
- X and Y are each independently an anilino group having 1 to 3 carboxy groups.
- the number of carboxy groups on the anilino group is usually 1 to 3, preferably 1 to 2.
- Specific examples of X and Y are each independently an anilino group having one carboxy group such as 2-carboxyanilino, 3-carboxyanilino, 4-carboxyanilino; And anilino group having two carboxy groups such as lino and 3,5-dicarboxyanilino; and anilino group having three carboxy groups such as 2,4,6-tricarboxyanilino and the like.
- X and Y in the above formula (1) are each independently preferably 3-carboxyanilino, 4-carboxyanilino or 3,5-dicarboxyanilino, both of which are the same and More preferred in some cases. More preferably, both are 3-carboxyanilino.
- b is 0 to 3.4
- c is 0.1 to 3.5
- the sum of b and c is 1.0 to 3.5.
- b is from 0.5 to 3.0, more preferably from 0.7 to 2.7, even more preferably from 1 to 2.5
- c is from 0.5 to 2.5, more preferably from 0.8. 8 to 2.5, more preferably 0.8 to 2, most preferably 0.8 to 1.7
- the sum of b and c is 1.0 to 3.5, preferably 1.5 to 3.5, more preferably 2.0 to 3.5.
- More preferable ratios of b and c are such that b is 0.7 to 2.7, c is 0.8 to 1.7, and the sum of b and c is 1.5 to 3.5, more preferably 2.0. ⁇ 3.5.
- the numbers of b and c are average values. As b increases, ozone resistance tends to improve, but bronzing tends to occur easily. What is necessary is just to adjust the number of b and c suitably, considering ozone resistance and bronzing property, and to select a ratio with a good balance.
- the porphyrazine coloring matter of the present invention represented by the above formula (1) or (2) comprises a compound represented by the above formula (3) or formula (5) and an organic amine represented by the above formula (4). It can be obtained by reacting in the presence of ammonia. The reaction conditions will be described later.
- the porphyrazine dye represented by the above formula (2) is preferable among the dyes represented by the above formula (1), and the rings A to D represented by broken lines in the above formula (1) are nitrogen-containing complex.
- the position of the nitrogen atom is specified. That is, the four rings containing Z 1 to Z 8 as ring constituent atoms correspond to the four rings A to D represented by the broken lines in the above formula (1).
- Z 1 to Z 8 each independently represent a nitrogen atom or a carbon atom (in the case of a carbon atom, the carbon atom has one hydrogen atom), and Z 1 and Z 2 , Z Of the four combinations of 3 and Z 4 , Z 5 and Z 6 and Z 7 and Z 8 , at least 1.0 is a combination of carbon atoms (that is, a combination in which the ring is a benzene ring), At least 0.5 of the remaining combinations are combinations in which the ring is a nitrogen-containing aromatic ring, that is, a combination of a nitrogen atom and a carbon atom or a combination of nitrogen atoms.
- the average values for the four combinations have the same meaning as the average values of the numbers of nitrogen-containing heteroaromatic rings and benzene rings in the rings A to D of the above formula (1), and preferred ranges are also included. Exactly the same. More specifically, the preferred number of combinations that form a nitrogen-containing heteroaromatic ring is usually 0.5 to 3.0, preferably 0.5 to 2.5, more preferably 0.5 on average. It is the combination which is thru
- the average number of combinations of nitrogen-containing heteroaromatic rings is 0.50 to 2.0, or 0.50 to 1.5, and in some cases 0.70 to A case where the number is 1.5 can be mentioned, in which case the remainder is a benzene ring.
- E, X, Y, b and c in the formula (2) are the same as those in the formula (1), including preferable ones.
- Z 1 to Z 8 is a carbon atom, the carbon atom has one hydrogen atom.
- the compound represented by the free acid of formula (1) or formula (2) can also form a salt by utilizing a carboxy group in the molecule.
- all the compounds represented by the formula (1) or the formula (2) when expressed in the form of a free acid are included in the present invention, and the compounds that form salts as described above are also included. It is included in the present invention.
- the salt of the compound represented by Formula (1) or Formula (2) is preferably an inorganic or organic cation salt.
- Examples of salts include alkali metal salts, alkaline earth metal salts and ammonium salts.
- Preferred alkali metal salts are lithium, sodium and potassium salts.
- Examples of the alkaline earth metal of the alkaline earth metal salt include calcium and magnesium.
- the organic cation salt includes a cation of an organic amine, that is, an onium salt of an organic amine.
- the organic amine include lower alkylamines having 1 to 3 carbon atoms such as methylamine and ethylamine, and monoamines such as monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, and triisopropanolamine. , Di or tri (lower alkanol having 1 to 4 carbon atoms) amines.
- Other salts include ammonium salts.
- preferable salts include alkali metal salts such as sodium salt, potassium salt, and lithium salt; mono-, di- or tri-, such as monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, and triisopropanolamine. (C1-C4 lower alkanol) amine onium salts; and ammonium salts.
- rings A to D, E, X, and Y in the porphyrazine dye represented by the formula (1) of the present invention are shown in the following Table 1, but the porphyrazine dye of the present invention is shown in the following example. It is not limited. Further, when the nitrogen-containing heteroaromatic ring corresponding to the rings A to D is a pyridine ring, there are positional isomers of nitrogen atoms as described later. Accordingly, Table 1 below includes some of these isomers. In addition, although there are many isomers not illustrated, the present invention includes any isomers. In addition, when synthesizing the dye represented by the formula (1) of the present invention, positional isomers and other by-products are mixed in addition to the main components as described later. There is no particular problem.
- the compound represented by the following formula (6) is, for example, a 6-membered nitrogen-containing heteroaromatic dicarboxylic acid derivative (meaning dicarboxylic acid or a derivative thereof) having aromaticity and a phthalic acid derivative in the presence of a catalyst and a copper compound. It is obtained by reacting with (which means phthalic acid or a derivative thereof). By changing the molar ratio during the reaction of each derivative, the number of nitrogen-containing heteroaromatic rings and the number of benzene rings in rings A to D can be adjusted.
- the nitrogen-containing heteroaromatic dicarboxylic acid derivative is used in a range of 0.125 to 0.75 mol
- the phthalic acid derivative is used in a range of 0.25 to 0.875 mol.
- the target compound can be obtained by adjusting to such a ratio.
- the nitrogen-containing heteroaromatic dicarboxylic acid derivative may be used at a ratio of 0.25 mol and the phthalic acid derivative at a ratio of 0.75 mol.
- the nitrogen-containing heteroaromatic dicarboxylic acid derivative a reactive group derived from a carboxyl group or a carboxyl group at two adjacent positions (an acid amide group, an imide group, an acid anhydride group, a carbonitrile group, etc.), respectively.
- 6-membered nitrogen-containing heteroaromatic dicarboxylic acid derivatives specifically 6-membered nitrogen-containing heteroaromatic dicarboxylic acids and acid amides, acid imides, acid anhydrides or carbonitriles derived therefrom. It is done.
- dicarboxylic acid compounds such as quinolinic acid, 3,4-pyridinedicarboxylic acid, 2,3-pyrazinedicarboxylic acid; quinolinic anhydride, 3,4-pyridinedicarboxylic anhydride, 2,3-pyrazinedicarboxylic acid Acid anhydride compounds such as acid anhydrides; Dicarboxyamide compounds such as pyridine-2,3-dicarboxamide; Dicarboxylic acid monoamide compounds such as pyrazine-2,3-dicarboxylic acid monoamide; Acid imide compounds such as quinolinic acid imide And dicarbonitrile compounds such as pyridine-2,3-dicarbonitrile and pyrazine-2,3-dicarbonitrile.
- phthalic acid derivative examples include phthalic acid, phthalic anhydride, phthalamide, phthalamic acid, phthalimide, phthalonitrile, 1,3-diiminoisoindoline, and 2-cyanobenzamide.
- the nitrile method is a method using a dicarbonitrile compound such as pyridine-2,3-dicarbonitrile, pyrazine-2,3-dicarbonitrile, phthalonitrile and the like as a raw material.
- the Weiler method is a dicarboxylic acid compound such as phthalic acid, quinolinic acid, 3,4-pyridinedicarboxylic acid, 2,3-pyrazinedicarboxylic acid; phthalic anhydride, quinolinic anhydride, 3,4-pyridinedicarboxylic anhydride, Acid anhydride compounds such as 2,3-pyrazine dicarboxylic acid anhydride; dicarboxyamide compounds such as phthalic acid amide and pyridine-2,3-dicarboxamide; phthalamic acid, pyrazine-2,3-dicarboxylic acid monoamide and the like Dicarboxylic acid monoamide compounds; and acid imide compounds such as phthalic acid imide and quinolinic acid imide; In the Weiler method, addition of urea is essential, and the amount of urea used is 5 to 100 times the amount of a total of 1 mol of the nitrogen-containing heteroaromatic dicarboxylic acid derivative and the phthal
- rings A, B, C and D represent the same meaning as described above.
- the reaction is carried out in the presence of a solvent.
- a solvent in the nitrile method an organic solvent having a boiling point of 100 ° C. or higher, more preferably 130 ° C. or higher is used.
- Specific examples of the solvent in the nitrile method include n-amyl alcohol, n-hexanol, cyclohexanol, 2-methyl-1-pentanol, 1-heptanol, 1-octanol, 2-ethylhexanol, N, N-dimethylamino Examples include ethanol, benzyl alcohol, ethylene glycol, propylene glycol, trichlorobenzene, chloronaphthalene, nitrobenzene, quinoline, sulfolane, and urea.
- an aprotic organic solvent having a boiling point of 150 ° C. or higher, more preferably 180 ° C. or higher is used.
- Specific examples of the solvent in the Weiler method include trichlorobenzene, chloronaphthalene, nitrobenzene, quinoline, sulfolane and urea.
- the amount of the solvent used is 1 to 100 times the total amount of the nitrogen-containing heteroaromatic dicarboxylic acid derivative and the phthalic acid derivative.
- Urea is not an organic solvent and is a solid at room temperature, but its melting point is 132 ° C., and therefore it can be preferably used as a solvent in each of the above reactions when it is reacted at a temperature higher than this.
- cyclic bases such as quinoline and 1,8-diazabicyclo [5,4,0] -7-undecene; amines such as tributylamine, ammonia and N, N-dimethylaminoethanol; and Alkali metal alcoholates such as sodium ethoxide and sodium methoxide; and the like.
- amines such as tributylamine, ammonia and N, N-dimethylaminoethanol
- Alkali metal alcoholates such as sodium ethoxide and sodium methoxide; and the like.
- the catalyst in the Weiler method include ammonium molybdate and boric acid.
- the amount of the catalyst added is 0.001 to 1 times the molar amount of the total of 1 mol of the nitrogen-containing heteroaromatic dicarboxylic acid derivative and the phthalic acid derivative.
- the copper compound examples include copper metal, or copper compounds such as copper halides, carboxylates, sulfates, nitrates, acetylacetonates or complexes. Specific examples of these copper compounds include copper chloride, copper bromide, copper acetate, copper acetylacetonate and the like. The amount of the copper compound used is 0.15 to 0.35 moles per mole of the total of the nitrogen-containing heteroaromatic dicarboxylic acid derivative and the phthalic acid derivative.
- the reaction temperature is usually 100 to 200 ° C, preferably 130 to 170 ° C.
- the reaction temperature is 150 to 300 ° C, preferably 170 to 220 ° C.
- the reaction time varies depending on the reaction conditions, but is usually 1 to 40 hours. After completion of the reaction, the compound represented by the above formula (6) is obtained by filtration, washing and drying.
- the main component of the product is copper dibenzobis (2,3-pyrido) porphyrazine, and five kinds of isomers having different positions of the pyridine ring and the nitrogen atom of the pyridine ring [ The following formulas (7-A) to (7-E)] are generated.
- copper tribenzo (2,3-pyrido) porphyrazine [formula (8) below], wherein one of the rings A to D in the formula (6) is a pyridine ring and the remaining three are benzene rings
- copper benzotris (2,3-pyrido) porphyrazine in which three of the rings A to D are pyridine rings and the other one is a benzene ring, is by-produced.
- the copper benzotris (2,3-pyrido) porphyrazine also contains positional isomers of the nitrogen atom of the pyridine ring [formula (9-A) to (9-D) below], so that the product is a complex mixture. It becomes.
- the compound of formula (6) obtained by the above synthesis method is substantially It is a mixture of these multiple compounds.
- the mixture is copper. Used as dibenzobis (2,3-pyrido) porphyrazine.
- the ratio of the nitrogen-containing heteroaromatic ring and the benzene ring contained in the compound of formula (6) can be determined by performing analysis such as elemental analysis, for example. Even when two of the rings A to D are nitrogen-containing heteroaromatic rings other than the pyridine ring, such as pyrazine rings, the corresponding nitrogen-containing heteroaromatics such as 2,3-pyrazinedicarboxylic acid are used instead of the quinolinic acid.
- a compound in which two of rings A to D are nitrogen-containing heteroaromatic rings other than a pyridine ring, such as a pyrazine ring, and the remaining two are benzene rings by synthesizing according to the above using a ring dicarboxylic acid derivative Can be obtained. Further, among the rings A to D, compounds having different ratios such as the compound of the formula (6) in which the nitrogen-containing heteroaromatic ring has an average value of 0.5 to 3.0 and the remainder is a benzene ring.
- the compound is obtained by the same synthesis method as described above by appropriately changing the use ratio of the nitrogen-containing heteroaromatic dicarboxylic acid derivative and the phthalic acid derivative. be able to.
- the compound represented by the formula (3) or the formula (5) can be obtained by chlorosulfonating the compound represented by the formula (6) in chlorosulfonic acid.
- the compound represented by the formula (6) can be obtained by sulfonating in a sulfuric acid or fuming sulfuric acid and then converting the sulfo group to a chlorosulfo group with a chlorinating agent.
- the chlorosulfo group or sulfo group thus obtained is introduced onto the benzene ring in rings A to D in the compound represented by the formula (6), and is not introduced onto the heteroaromatic ring group in rings A to D. .
- the number (n) of SO 2 Cl in the compound of the formula (3) is 1.0 to 3.5 on average depending on the number of benzene rings in the rings A to D of the compound of the formula (3). is there.
- N in the formula (3) is preferably 1.5 to 3.5, more preferably 2.0 to 3.5.
- N in the formula (5) is the same as that in the formula (3), and the number of n is an average value of 1.0 to 3.5, preferably 1.5 to 3.5, more preferably 2.0. ⁇ 3.5.
- a sulfo group represented by the following formula (10) can be formed by condensation ring closure using sulfophthalic acid having a sulfo group and quinolinic acid in advance.
- the desired compound represented by the formula (3) can also be obtained by synthesizing a compound having the compound and then converting the sulfo group to a chlorosulfo group.
- the compound of the formula (5) can also be synthesized in the same manner by using the corresponding raw material compound.
- rings A to D and n represent the same meaning as in formula (3).
- the chlorosulfonation of the compound of the formula (6) is usually carried out using 3 to 20 times by weight, preferably 5 to 10 times by weight of chlorosulfonic acid as a solvent.
- the reaction temperature is usually 100 to 150 ° C., preferably 120 to 150 ° C.
- the reaction time varies depending on the reaction conditions such as the reaction temperature, but is usually 1 to 10 hours. In this case, all of the substituents of the reaction product obtained are usually not chlorosulfonated, leaving unreacted sulfo groups.
- a chlorinating agent such as thionyl chloride
- thionyl chloride sulfuryl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride and the like.
- the addition amount of the chlorinating agent is about 0.5 to 10 equivalents, preferably about 0.5 to 5 equivalents, relative to the chlorosulfo group of the target compound.
- Conversion of the sulfo group to the chlorosulfo group in the sulfo-substituted copper porphyrazine dye represented by the formula (10) can be performed by reacting the compound with the chlorinating agent in the same manner as described above.
- the reaction solvent used in the chlorination reaction include sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, benzene, toluene, nitrobenzene, chlorobenzene, N, N-dimethylformamide, N, N-dimethylacetamide, and the like. It is not limited.
- the porphyrazine dye of the present invention represented by the above formula (1) can be obtained by reacting in an aqueous solvent, usually at pH 8 to 10, 5 to 70 ° C., and 1 to 20 hours.
- aminating agent used in the reaction ammonia or a compound that generates ammonia in the above reaction (ammonia generating compound) can be used.
- ammonium salt compounds such as ammonium chloride and ammonium sulfate; urea, aqueous ammonia, ammonia gas Etc.
- the reaction is usually performed in an aqueous solvent as described above.
- the usage-amount of the organic amine represented by the said Formula (4) is normally 1 time mol or more of the theoretical value according to the value of c with respect to 1 mol of compounds represented by the said Formula (3).
- it varies depending on the reactivity of the organic amine and the reaction conditions, and is not limited thereto.
- the values of b and c in the porphyrazine coloring matter of the present invention can be adjusted by the amount of the organic amine represented by the formula (4) during the synthesis reaction. For example, in order to obtain a compound in which b is 1.0 in formula (1), c is 1.5, and the sum of b and c is 2.5, n in formula (3) is 2.
- the above synthesis reaction may be carried out using 1.5 mol of organic amine represented by the formula (4) or a small excess thereof per 1 mol of the compound of 5.
- the product obtained by the synthesis reaction of the compound represented by the formula (3) and the organic amine represented by the formula (4) is substantially a mixture of compounds having various values of b and c. . Therefore, the values of b and c in the formulas (1) and (2) are average values of b and c in these mixtures.
- a method for producing the organic amine represented by the formula (4) will be described.
- 0.95 to 1.1 mol of carboxy-substituted aniline corresponding to X and 1 mol of 2,4,6-trichloro-S-triazine (cyanuric chloride) in water usually pH 3 to 7, 5 to 40 ° C.
- the reaction is carried out for 2 to 12 hours to obtain a primary condensate.
- 0.95 to 1.5 mol of carboxy-substituted aniline corresponding to Y is usually added to the reaction solution, and reacted under the conditions of pH 4 to 10, 5 to 80 ° C., and 0.5 to 12 hours. A subcondensate is obtained.
- an alkylenediamine represented by the following formula (11) is added to the reaction solution, and the reaction is usually carried out under conditions of pH 9 to 12, 5 to 90 ° C., 0.5 to 8 hours.
- a compound represented by the formula (4) is obtained.
- the pH of the reaction solution in each condensation reaction is usually adjusted using an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, or an alkali metal carbonate such as sodium carbonate or potassium carbonate.
- the order of condensation is appropriately determined according to the reactivity of various compounds, and is not limited to the above.
- the porphyrazine coloring matter of the present invention represented by the formulas (1) and (2) includes a compound represented by the formula (3) or the formula (5), an organic amine represented by the formula (4), and In the presence of ammonia. Since this synthesis reaction does not require anhydrous conditions, a part of the chlorosulfonyl compound represented by formula (3) or formula (5) is hydrolyzed by water mixed in the reaction system and converted into a sulfonic acid group. It is theoretically conceivable that the resulting compound is produced as a by-product and mixed into the dye represented by the formulas (1) and (2).
- the copper porphyrazine ring (Pz) is dimerized (for example, Pz-L-) via the divalent linking group (L). Impurities that form Pz) or trimers are by-produced, and the by-products may be mixed into the reaction product.
- the divalent linking group represented by L -SO 2 -, - SO 2 -NH-SO 2 - include, by-products of these two L are combined in the case of a trimer Sometimes it is formed.
- the porphyrazine coloring matter of the present invention thus obtained can be separated by filtration or the like after aciding out or salting out, if necessary.
- salting out for example, it is preferably carried out in the range of acidic to alkaline, preferably pH 1-11.
- the temperature for salting out is not particularly limited, but is usually 40 to 80 ° C., preferably 50 to 70 ° C. More specifically, it is preferable to salt out by heating the reaction solution containing the porphyrazine coloring matter of the present invention to the above temperature and then adjusting the pH to the above range by adding sodium chloride or ammonium chloride.
- the porphyrazine dye of the present invention synthesized by the above method can be obtained in the form of a free acid or a salt thereof.
- a free acid for example, acid precipitation may be performed.
- salting out may be performed to form a salt.
- a normal salt exchange method such as a method of adding a desired organic or inorganic base to a free acid may be used.
- 0.5 to 3.0, more preferably 0.5 to 2.5, and still more preferably 0.5 to 2.0 are pyridine rings or pyrazine rings (more preferably Is a pyridine ring, and the remaining 1.0 to 3.5, more preferably 1.5 to 3.5, and still more preferably 2.0 to 3.5 are benzene rings.
- E is a C2-C4 alkylene group, more preferably an ethylene group or a propylene group
- X and Y are independently anilino groups having 1 to 3 carboxy groups, more preferably anilino groups having 1 or 2 carboxy groups, more preferably 3-carboxyanilino, 4-carboxyanilino or 3,5 -Dicarboxyanilino, particularly preferably 3-carboxyanilino
- b is 0 to 3.4 and c is 0.1 to 3.5, preferably b is 0.5 to 3.0, and c is 0.5 to 2.5. Yes;
- the sum of b and c is 1.5 to 3.5, more preferably 2.0 to 3.5, and still more preferably 2.5 to 3.5.
- a combination of a more preferable one with another is more preferable, and a combination of two or three more preferable ones is more preferable.
- preferred porphyrazine dyes are as follows.
- 0.5 to 3.0 is a pyridine ring or a pyrazine ring, and the remaining is 1.0 to 3.5
- E is a C2-C4 alkylene group
- X and Y are each independently an anilino group having 1 to 3 carboxy groups; Both are average values, b is from 0 to 3.4, in some cases from 0 to 3.2, c is from 0.1 to 3.5, in some cases from 0.1 to 3.3, and b and c
- the ink composition of the present invention is characterized by containing the porphyrazine coloring matter of the present invention.
- the porphyrazine coloring matter of the present invention that can be produced by the above method exhibits a clear cyan color. Therefore, ink compositions containing these are also mainly used as cyan ink.
- the ink composition is used as a low dye density cyan ink (referred to as light cyan ink or photocyan ink) used to smoothly reproduce the gradation portion of an image or to reduce the graininess of a light color area. May be.
- the ink composition of the present invention is prepared using water as a medium.
- Cl contained as impurities in the porphyrazine coloring matter of the present invention - the content of anions and SO 4 2-like less is preferred.
- it is 1 mass% or less, Preferably it is 0.5% or less, More preferably, it is 0.1% or less.
- the lower limit may be below the detection limit of the analytical instrument, that is, 0%.
- Cl - in the production of porphyrazine dye and SO 4 2-less invention conventional methods using a reverse osmosis membrane for example, or a dried product or a wet cake of the dye was stirred in a mixed solvent secondary alcohol and water Desalting treatment may be performed by a method such as filtration, drying and the like.
- the alcohol used at this time is a lower alcohol having 1 to 4 carbon atoms, preferably an alcohol having 1 to 3 carbon atoms, more preferably methanol, ethanol or 2-propanol.
- a method of heating to near the boiling point of the alcohol used and then cooling to desalinate can be employed.
- Cl - and SO 4 content of 2 for example can be measured by ion chromatography.
- the porphyrazine coloring matter of the present invention contained as a coloring matter in the ink composition is the coloring matter except for copper (ion) contained as the central metal atom.
- a low content of heavy metals (ions) such as zinc and iron, and metals (ions) such as calcium and silica contained as impurities in the total mass.
- the standard of the content is, for example, about 500 ppm or less for each of heavy metals (ions) such as zinc and iron and metals (ions) such as calcium and silica in the purified and dried product of the porphyrazine coloring matter of the present invention.
- the contents of heavy metals (ions) and metals (ions) are measured by ion chromatography, atomic absorption, or ICP (Inductively Coupled Plasma) emission analysis.
- the ink composition of the present invention contains the porphyrazine coloring matter of the present invention in a total mass of 0.1 to 8% by mass, preferably 0.3 to 6% by mass, the balance being water, It may contain a water-soluble organic solvent and other ink additives (ink preparation agents).
- the ink composition of the present invention preferably further contains a water-soluble organic solvent as necessary within a range that does not impair the effects of the present invention.
- the water-soluble organic solvent is used for the purposes of dye dissolution, drying prevention (wetting agent), viscosity adjustment, penetration promotion, surface tension adjustment, defoaming and the like.
- the ink preparation agents for example, antiseptic / antifungal agents, pH adjusters, chelating reagents, rust preventive agents, UV absorbers, viscosity adjusters, dye dissolving agents, antifading agents, emulsion stabilizers, surface tension adjusters Further, additives such as an antifoaming agent, a dispersing agent and a dispersion stabilizer may be contained.
- the water-soluble organic solvent is 0 to 60% by mass, preferably 5 to 50%, more preferably 10 to 50% by mass, and the ink preparation agent is 0 to 20% by mass with respect to the total amount of the ink composition. %, Preferably 0 to 15% by mass. The balance is water.
- water-soluble organic solvent examples include C1-C4 alkanols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, and tert-butanol; N, N-dimethyl Carboxylic acid amides such as formamide or N, N-dimethylacetamide; 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidin-2-one or 1,3-dimethylhexahydropyrimido-2- Heterocyclic ketones such as ON; ketones or ketoalcohols such as acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one; cyclic ethers such as tetrahydrofuran, dioxane; ethylene glycol, 1,2- or 1,3 -Propylene glycol, 1,
- water-soluble organic solvent preferred as the water-soluble organic solvent are isopropanol, glycerin, mono-, di- or triethylene glycol, dipropylene glycol, 2-pyrrolidone, N-methyl-2-pyrrolidone and butyl carbitol. More preferred are isopropanol, glycerin, diethylene glycol, N-methyl-2-pyrrolidone and butyl carbitol. These water-soluble organic solvents are used alone or in combination.
- antiseptic / antifungal agents examples include organic sulfur, organic nitrogen sulfur, organic halogen, haloallylsulfone, iodopropargyl, N-haloalkylthio, benzothiazole, nitrile, pyridine, 8- Oxyquinoline, isothiazoline, dithiol, pyridine oxide, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiadiazine, anilide, adamantane, dithiocarbamate, brominated indanone And compounds such as benzyl bromacetate and inorganic salts.
- An example of the organic halogen compound is sodium pentachlorophenol.
- Examples of pyridine oxide compounds include sodium 2-pyridinethiol-1-oxide.
- Examples of the isothiazoline compound include 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 5- And chloro-2-methyl-4-isothiazolin-3-one magnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-one calcium chloride, 2-methyl-4-isothiazolin-3-one calcium chloride It is done.
- antiseptic and antifungal agents include sodium acetate, sodium sorbate, sodium benzoate and the like (for example, trade names Proxel RTM GXL (S), Proxel RTM XL-2 (S) manufactured by Avecia) and the like.
- any substance can be used as long as it can control the pH of the ink in the range of 6.0 to 11.0 for the purpose of improving the storage stability of the ink.
- alkanolamines such as diethanolamine and triethanolamine
- hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide
- ammonium hydroxides or alkali metal such as lithium carbonate, sodium carbonate and potassium carbonate Carbonate; and the like.
- Examples of the chelating reagent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uracil diacetate and the like.
- Examples of the rust preventive include acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite.
- the ultraviolet absorber examples include benzophenone compounds, benzotriazole compounds, cinnamic acid compounds, triazine compounds, and stilbene compounds. Further, a compound that absorbs ultraviolet rays typified by a benzoxazole-based compound and emits fluorescence, a so-called fluorescent brightener can also be used.
- viscosity modifier examples include water-soluble polymer compounds in addition to water-soluble organic solvents, such as polyvinyl alcohol, cellulose derivatives, polyamines, and polyimines.
- dye solubilizer examples include urea, ⁇ -caprolactam, ethylene carbonate and the like.
- the anti-fading agent is used for the purpose of improving image storage stability.
- various organic and metal complex antifading agents can be used.
- Organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocyclic compounds, etc.
- nickel complexes and zinc complexes There are nickel complexes and zinc complexes.
- Examples of the surface tension adjusting agent include a surfactant, and examples thereof include an anionic surfactant, an amphoteric surfactant, a cationic surfactant, and a nonionic surfactant.
- Anionic surfactants include alkyl sulfocarboxylates, ⁇ -olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acyl amino acids or salts thereof, N-acyl methyl taurates, alkyl sulfates polyoxyalkyl ether sulfates Salt, alkyl sulfate polyoxyethylene alkyl ether phosphate, rosin acid soap, castor oil sulfate ester, lauryl alcohol sulfate ester, alkylphenol type phosphate ester, alkyl type phosphate ester, alkylaryl sulfonate, diethylsulfate , Diethylhexylsyl sulfo
- Examples of the cationic surfactant include 2-vinylpyridine derivatives and poly-4-vinylpyridine derivatives.
- Amphoteric surfactants include lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine, imidazoline derivatives, etc. is there.
- Nonionic surfactants include ethers such as polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether; Ester systems such as polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate; 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5-di Chill-1-hexyne-3-ones such as acetylene glycol (alcohol) based, such as ol.
- Other specific examples include Surfinol R
- antifoaming agent a highly oxidized oil-based, glycerin fatty acid ester-based, fluorine-based, or silicone-based compound is used as necessary.
- the surface tension of the ink composition of the present invention is usually 25 to 70 mN / m, more preferably 25 to 60 mN / m. Further, the viscosity of the ink of the present invention is preferably 30 mPa ⁇ s or less, and more preferably adjusted to 20 mPa ⁇ s or less.
- the water used for preparing the ink composition is preferably water with few impurities, such as ion exchange water or distilled water. Furthermore, if necessary, fine filtration may be performed using a membrane filter to remove impurities. When used as ink for an inkjet printer, it is preferable to perform fine filtration.
- the pore diameter of the filter for performing microfiltration is usually 1 ⁇ m to 0.1 ⁇ m, preferably 0.8 ⁇ m to 0.1 ⁇ m.
- the ink composition of the present invention can be used not only for forming a single color image but also for forming a full color image.
- a full-color image it is also used as an ink set of three primary colors with magenta ink and yellow ink, and further as an ink set of four colors with black ink added thereto.
- the ink set is used in combination with light magenta ink, blue ink, green ink, orange ink, dark yellow ink, gray ink, and the like.
- aryl or heteroarylazo dyes having phenols, naphthols, anilines, heterocycles such as pyrazolone and pyridone as coupling components hereinafter referred to as coupler components
- coupler components azomethine dyes; benzylidene dyes and monomethine oxo Methine dyes such as knol dyes; quinone dyes such as naphthoquinone dyes and anthraquinone dyes; and other dye types such as quinophthalone dyes; nitro / nitroso dyes; acridine dyes; acridinone dyes, etc. be able to.
- magenta ink dyes can be used.
- aryl or heteroaryl 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 Methine dyes such as dyes and oxonol dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes and xanthene dyes; quinone dyes such as naphthoquinone, anthraquinone and anthrapyridone; A ring dye etc. can be mentioned.
- examples of the black pigment include azo dyes such as disazo, trisazo, and tetraazo, and carbon black dispersions.
- the ink composition of the present invention can be used in recording methods such as printing, copying, marking, writing, drawing, stamping, and the like, and is particularly suitable for use in an ink jet recording method.
- the ink composition prepared as described above is placed in an ink container or the like, and energy is given to the ink composition, whereby the ink composition is ejected as ink droplets, and a known recording target is recorded.
- Form images on materials such as plain paper, resin-coated paper, inkjet paper, glossy paper, glossy film, electrophotographic co-paper, fiber and cloth (cellulose, nylon, wool, etc.), glass, metal, ceramics, leather, etc. Is the method.
- a container also referred to as an ink tank or the like
- the ink jet printer include a piezo printer using mechanical vibration and a bubble jet RTM printer using bubbles generated by heating.
- 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 recording material may be before, after or at the same time as applying the colorant. Therefore, according to the recording method of the present invention, the polymer latex may be added to the recording material or the ink, or the polymer latex may be applied to the recording material as a single liquid. good.
- the colored body of the present invention is obtained by coloring a material to be colored with the porphyrazine coloring matter of the present invention or the ink composition of the present invention containing the same using an inkjet printer or the like.
- the material to be colored is not particularly limited as long as it is an article that can be colored by the recording material and other ink jet printers.
- Examples of the material to be colored include information transmission sheets such as paper and film, fibers and cloth (cellulose, nylon, wool, etc.), leather, and a color filter base material.
- the information transmission sheet is preferably a surface-treated sheet, specifically, a sheet, a synthetic paper, a film or other base material provided with an ink receiving layer.
- the ink receiving layer is formed by, for example, impregnating or coating the above-mentioned base material with a cationic polymer, and by adding inorganic fine particles capable of absorbing pigments in ink such as porous silica, alumina sol, and special ceramics to polyvinyl alcohol or polyvinyl alcohol. It is provided by coating the surface of the substrate together with a hydrophilic polymer such as pyrrolidone.
- the information transmission sheet provided with such an ink receiving layer is usually called ink jet dedicated paper (film), glossy paper (film) or the like. Plain paper refers to paper that is not particularly provided with an ink-receiving layer, and many different types of paper are commercially available depending on the application.
- plain paper for inkjet, double-sided high-quality plain paper manufactured by Seiko Epson Corporation; color plain paper manufactured by Canon Inc .; Multipurpose Paper, All-in-one Printing Paper manufactured by Hewlett Packard; and so on.
- PPC paper whose use is not particularly limited to ink jet printing is also plain paper.
- the ink composition of the present invention is particularly excellent in water resistance on plain paper as described above, and for this reason, it is particularly suitable for plain paper. In addition, it has excellent resistance to light, ozone, humidity and friction. Excellent water resistance on inkjet special paper, special film, glossy paper or glossy film with an ink receiving layer for inkjet printing, and light resistance, ozone resistance, moisture resistance on the information transmission sheet Excellent in wear resistance and abrasion resistance.
- the ink according to the present invention does not precipitate or separate during storage. Further, when the ink according to the present invention is used in ink jet recording, the ejector (ink head) is not blocked. The ink according to the present invention does not cause a change in physical properties even when used for a relatively long time and under constant recirculation by a continuous ink jet printer or intermittently by an on-demand ink jet printer.
- the ink of the present invention has a clear cyan color, and is particularly excellent in water resistance and can provide a recorded matter excellent in light resistance and ozone resistance.
- it can also be used with other yellow, magenta, and other inks such as green, red, orange, and blue, which are excellent in water resistance, light resistance and ozone resistance. It is possible to express a color tone in a wide visible region, and it is possible to obtain a recorded matter that is particularly excellent in water resistance and excellent in light resistance and ozone resistance.
- Example 1 (1) Synthesis of a compound in which, in formula (6), among rings A to D, 1.5 on average are pyridine rings and 2.5 are benzene rings.
- 250 parts of sulfolane, 18.4 parts of phthalimide, 12.5 parts of quinolinic acid, 72.0 parts of urea, 8.8 parts of copper (II) chloride dihydrate (purity 97.0%) Then, 1.0 part of ammonium molybdate was added, the liquid temperature was raised to 200 ° C., and the reaction was carried out at the same temperature for 5 hours. After completion of the reaction, the reaction solution was cooled to 65 ° C., 200 parts of methanol was added thereto, and the precipitated solid was separated by filtration.
- the obtained solid was washed with 150 parts of methanol and subsequently with 200 parts of hot water to obtain 72.2 parts of a wet cake.
- the total amount of the obtained wet cake was added to 500 parts of 5% hydrochloric acid, and then the liquid temperature was raised to 60 ° C. and kept at that temperature for 1 hour.
- the precipitated solid was separated by filtration at room temperature and washed with 200 parts of water to obtain a wet cake.
- the total amount of the obtained wet cake was added to 500 parts of 10% aqueous ammonia, and the liquid was kept at 60 ° C. for 1 hour.
- the precipitated solid was separated by filtration, and the obtained solid was washed successively with 300 parts of water and 100 parts of methanol to obtain 33.6 parts of a wet cake.
- the obtained wet cake was dried at 80 ° C. to obtain 19.8 parts of the target compound as a blue solid.
- Cyanuric chloride (18.4 parts) and Leocol RTM TD-90 (surfactant, manufactured by Lion Corporation) were added to 150 parts of ice water, and the mixture was stirred at 10 ° C. or lower for 30 minutes.
- 28.0 parts of 3-carboxyaniline (purity 99%) was added thereto, and the pH was maintained at 6.0 to 7.0 using a 10% aqueous sodium hydroxide solution.
- the reaction was carried out for 30 hours, 20 to 25 ° C. for 1 hour and 30 minutes, and 40 to 45 ° C. for 1 hour and 30 minutes. After 60 parts of ethylenediamine was added dropwise to the reaction solution and reacted at room temperature overnight, the reaction solution was adjusted to pH 5.0 using concentrated hydrochloric acid.
- the total amount of the reaction solution was 1000 parts.
- 100 parts of sodium chloride was added, stirred for 30 minutes, and the precipitated solid was separated by filtration to obtain 207.5 parts of a wet cake.
- the pH was adjusted to 9.0 using a 10% aqueous sodium hydroxide solution.
- the total amount of the solution was 850 parts.
- This solution was adjusted to pH 5.0 with concentrated hydrochloric acid and stirred for 30 minutes to precipitate a solid.
- the precipitated solid was separated by filtration and washed with 200 parts of water to obtain 221 parts of a wet cake.
- the obtained wet cake was dried to obtain 40.1 parts of white powder of the target compound of the above formula (12).
- the total amount of the reaction solution at this time was 230 parts.
- the reaction solution was raised to 50 ° C. and adjusted to pH 3.0 with concentrated hydrochloric acid over 20 minutes.
- the obtained precipitate was separated by filtration and washed with 200 parts of water to obtain 56.0 parts of a wet cake.
- the free acid of the porphyrazine dye of the present invention represented by the above formula (13) (b is a dye having 1.24 and c is 1.26) is converted into a blue powder.
- 11.8 parts were obtained.
- Example 2 (1) Synthesis of a compound represented by the following formula (14) [X and Y in formula (4) are 4-carboxyanilino and E is ethylene].
- the total amount of the reaction solution was 1000 parts.
- 100 parts of sodium chloride was added, stirred for 30 minutes, and the precipitated solid was separated by filtration to obtain 405.5 parts of a wet cake.
- the pH was adjusted to 9.0 using a 10% aqueous sodium hydroxide solution to obtain a solution.
- the total amount of the solution was 900 parts.
- This solution was adjusted to pH 5.0 with concentrated hydrochloric acid, stirred for 30 minutes, and the precipitated solid was separated by filtration.
- the obtained solid was washed with 200 parts of water to obtain 189.7 parts of a wet cake.
- the obtained wet cake was dried to obtain 39.2 parts of a white powder of the target compound represented by the above formula (14).
- Example 1 (2) In 100 parts of ice water, a wet cake obtained in the same manner as in Example 1 (2) (among the rings A to D in the formula (3), an average of 1.5 pyridine rings and 2.5 40.0 parts of a wet cake of a compound having a benzene ring and n of 2.5) was added, and the suspension was stirred at 5 ° C. or lower. Ten minutes later, while maintaining the liquid temperature at 10 ° C. or lower, 2.5 parts of 28% aqueous ammonia and 6.2 parts of the compound represented by the formula (15) in 60 parts of water were dissolved. Both were added to this suspension. Furthermore, 28% aqueous ammonia was added thereto to adjust the pH to 9.0.
- Example 3 (1) Synthesis of a compound represented by the following formula (16) [X and Y in formula (4) are 3,5-dicarboxyanilino and E is ethylene].
- Cyanuric chloride (18.4 parts) and Leocol RTM TD-90 (surfactant) (0.2 parts) were added to 330 parts of ice water and stirred at 10 ° C. or lower for 30 minutes.
- 36.3 parts of 3,5-dicarboxyaniline (purity 99.3%) was added thereto, and the pH was adjusted to 7.0 to 7.5 using a 10% aqueous sodium hydroxide solution.
- the reaction was carried out at 5 ° C. for 1 hour, then at 25-30 ° C. for 3 hours, and further at 40-45 ° C. for 1 hour while adjusting the pH to 8.0-8.5.
- Example 2 40.0 parts of a wet cake obtained in the same manner as in Example 1 (2) was added to 100 parts of ice water, and this suspension was stirred at 5 ° C. or lower. Ten minutes later, while maintaining the liquid temperature at 10 ° C. or lower, both 2.5 parts of 28% aqueous ammonia and a solution obtained by dissolving 7.6 parts of the compound represented by the formula (21) in 60 parts of water. Was added to this suspension, and then 28% aqueous ammonia was added thereto to adjust the pH to 9.0. The same aqueous ammonia was added as appropriate, and while maintaining the same pH, the liquid temperature was raised to 20 ° C. over 1 hour, and the reaction liquid was held at the same temperature for 8 hours.
- the total amount of the reaction solution at this time was 230 parts.
- the temperature of the reaction solution was raised to 50 ° C. and adjusted to pH 4.0 with concentrated hydrochloric acid over 20 minutes.
- the precipitated solid was separated by filtration and washed with 200 parts of water to obtain 124.1 parts of a wet cake.
- the obtained wet cake was dried to obtain 26.6 parts of the free acid of the porphyrazine coloring matter of the present invention represented by the above formula (17) as a blue powder.
- Example 4 (1) Synthesis of a compound in which 1.0 on the average of the rings A to D in the formula (6) is a pyridine ring and 3.0 is a benzene ring.
- the liquid temperature was raised to 200 ° C., and the reaction liquid was kept at the same temperature for 5 hours.
- the reaction solution was cooled to 65 ° C., 200 parts of methanol was added thereto, and the precipitated solid was separated by filtration.
- the obtained solid was washed sequentially with 150 parts of methanol and 200 parts of warm water to obtain 74.2 parts of a wet cake.
- the liquid temperature was raised to 60 ° C., and the reaction liquid was held at the same temperature for 1 hour.
- the precipitated solid was separated by filtration and washed with 200 parts of water to obtain a wet cake.
- the total amount of the obtained wet cake was added to 500 parts of 10% aqueous ammonia, and then the reaction solution was held at 60 ° C. for 1 hour.
- the precipitated solid was separated by filtration and washed successively with 300 parts of water and 100 parts of methanol to obtain 36.6 parts of a wet cake.
- the obtained wet cake was dried at 80 ° C. to obtain 21.8 parts of the target compound as a blue solid. ⁇ max: 655.0 nm (in pyridine)
- Example 5 (1) Synthesis of a compound in which, among the rings A to D in the formula (6), an average value of 0.75 is a pyridine ring and 3.25 is a benzene ring.
- the liquid temperature was raised to 200 ° C., and the reaction liquid was reacted at the same temperature for 5 hours.
- the liquid temperature was cooled to 65 ° C., 200 parts of methanol was added to the reaction liquid, and the precipitated solid was separated by filtration.
- the solid obtained was washed successively with 150 parts of methanol and 200 parts of warm water to obtain 78.3 parts of a wet cake.
- the liquid temperature was raised to 60 ° C., and the reaction liquid was kept at the same temperature for 1 hour.
- the precipitated solid was separated by filtration and washed with 200 parts of water to obtain a wet cake.
- the total amount of the obtained wet cake was added to 500 parts of 10% aqueous ammonia, the liquid temperature was raised to 60 ° C., and the reaction liquid was held at the same temperature for 1 hour.
- the precipitated solid was separated by filtration and then washed successively with 300 parts of water and 100 parts of methanol to obtain 39.4 parts of a wet cake.
- the obtained wet cake was dried at 80 ° C. to obtain 24.3 parts of the target compound as a blue solid.
- the desired free acid of the porphyrazine dye of the present invention represented by the formula (13) (b is a dye having 2.29 and c is 0.96) is converted into a blue powder. As a result, 11.9 parts were obtained. ⁇ max: 611.5 nm (in aqueous solution)
- Example 6 Ink Preparation Examples 6 to 10 Using the porphyrazine coloring matter of the present invention obtained in Example 1 as a coloring matter and mixing each component at the composition ratio shown in Table 2 below to obtain the ink composition of the present invention, a 0.45 ⁇ m membrane filter The ink for inkjet recording for an evaluation test was prepared by removing contaminants by filtering with (1). The preparation of this ink is referred to as Example 6. As the water, ion exchange water was used, and an aqueous ammonia solution and water were added so that the pH of the ink composition was about 9.5 and the total amount was 100 parts. An ink was prepared in the same manner as in Example 6 except that the dyes obtained in Examples 2 to 5 were used instead of the porphyrazine dye of the present invention obtained in Example 1. The ink preparations are referred to as Examples 7 to 10, respectively.
- Comparative Example 1 Instead of the porphyrazine dye of the present invention obtained in Example 1 as the dye, a dye represented by the following formula (18) (CI Direct Blue 86) was used in the same manner as in Example 1, The ink of Comparative Example 1 was prepared.
- the sulfonic acid group in the dye is a mixture of those substituted at the 3-position of phthalocyanine, and the following formula (18) shows one of the possible structural formulas.
- This dye is known to be a sodium salt.
- Comparative Example 2 The sodium salt of the dye used in Comparative Example 1 was replaced with an ammonium salt according to a conventional method. Comparative Example 2 was carried out in the same manner as in Example 1 except that instead of the porphyrazine dye of the present invention obtained in Example 1 as the dye, the ammonium salt of the dye of Comparative Example 1 obtained by the above salt exchange was used. Ink was prepared.
- Comparative Example 3 Example 1 except that the dye described in Example 3 (2) of Patent Document 15 represented by the following formula (19) is used in place of the porphyrazine dye of the present invention obtained in Example 1 as the dye. Similarly, the ink of Comparative Example 3 was prepared.
- the dye described in Example 3 (2) of Patent Document 15 represented by the following formula (19) is used in place of the porphyrazine dye of the present invention obtained in Example 1 as the dye.
- the ink of Comparative Example 3 was prepared.
- the following formula (19) among the four 6-membered aromatic rings A to D, 1.5 are pyridine rings condensed at the 2-position and 3-position, and the remaining 2.5 are benzene rings. is there.
- Comparative Example 4 Instead of the porphyrazine dye of the present invention obtained in Example 1 as the dye, the same procedure as in Example 1 was conducted except that the dye described in Example 5 of Patent Document 15 represented by the following formula (20) was used.
- the ink of Comparative Example 4 was prepared.
- the following formula (20) among the four 6-membered aromatic rings A to D, 1.5 are pyridine rings condensed at the 2-position and 3-position, and the remaining 2.5 are benzene rings. is there.
- each comparative example shows that in all the water resistance tests, bleeding (water resistance test 1) and dye residual ratio are less than 50% (water resistance test 2). It was a very bad result.
- the inks of the respective examples gave good results in both cases of the water resistance tests 1 and 2, indicating that the water resistance of plain paper is extremely higher than that of the comparative examples.
- the porphyrazine coloring matter of the present invention has high water solubility and is suitable for the preparation of ink, particularly for the preparation of ink for ink jet recording, and the ink composition of the present invention containing the coloring matter is When recorded (printed or colored) on a recording material, the recorded material (printed material or colored product), particularly when recorded by inkjet, is excellent in various fastness properties, particularly recorded (printed or colored) on plain paper.
- the recorded matter (printed matter or colored product) is extremely excellent in water resistance, and is suitable for ink for ink jet recording.
- the porphyrazine coloring matter of the present invention is very useful as various recording ink coloring matters, particularly cyan coloring matter for ink jet inks, and the ink composition of the present invention is useful as ink for ink jet recording. is there.
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Abstract
Description
インクジェットのノズル詰まりは、ノズル付近でインク中の水分が、他の溶剤や添加剤よりも先に蒸発し、水分が少なく溶剤や添加剤が多いという組成状態になったときに色素が固化し析出することに由来するものが多い。よって、インク中の水分の蒸発により、インクが濃縮された場合においても固体が析出しにくいということが非常に重要な要求性能の一つである。そのため、溶剤や添加剤に対する高い溶解性も色素に求められる性質のひとつである。
〔例えば、Cu-Pc-(SO3Na)m(SO2NH2)n : m+n=1~4の混合物〕。
〔例えば、Cu-Pc-(CO2H)m(CONR1R2)n : m+n=0~4の数〕。
〔例えば、Cu-Pc-(SO3H)m(SO2NR1R2)n : m+n=0~4の数、且つ、m≠0〕。
〔例えば、Cu-Pc-(SO3H)l(SO2NH2)m(SO2NR1R2)n : l+m+n=0~4の数〕。
〔例えば、Cu-Pc-(SO2NR1R2)n : n=1~5の数〕。
〔置換基の置換位置を制御したフタロシアニン化合物、β-位に置換基が導入されたフタロシアニン系色素〕。
特許文献1に記載の染料は、特定の普通紙上での耐水性については優れているが、市場に出回る各種の普通紙の多くに対して耐水性が優れているとは言えず、その適用範囲は狭い。よって、より多くの種類の普通紙上で一様に優れた耐水性をもち、耐光性や色相、色濃度にも優れたシアン色素が求められていた。
特許文献10、13、14及び15等に開示された含窒素複素環とベンゼン環を有するベンゾピリドポルフィラジン系色素は、活性ガス耐性、耐光性、耐湿性、及び色相等を付与したものであるが、普通紙での耐水性の向上に触れているものはない。
即ち、本発明は、
(1)下記式(1)で表されるポルフィラジン色素又はその塩
Eはアルキレン基を表し、
X及びYはそれぞれ独立して、カルボキシ基を1乃至3個有するアニリノ基であり、
いずれも平均値でbは0から3.4、cは0.1から3.5であり、且つbおよびcの和は1.0から3.5である。]、
(2)含窒素複素芳香環が、ピリジン環またはピラジン環である上記(1)に記載のポルフィラジン色素又はその塩、
(3)下記式(3)で表される化合物と、下記式(4)で表される有機アミンとをアンモニア存在下で反応させて得られる上記(1)または(2)に記載のポルフィラジン色素又はその塩、
(4)破線で表される環A、B、C及びDの4つの環のうち、平均値で、0.5乃至3.0個がピリジン環またはピラジン環であり、且つ、残りのうち、1.0乃至3.5個がベンゼン環であり、
EがC2-C4アルキレン基であり、
X及びYはそれぞれ独立して、カルボキシ基を1乃至3有するアニリノ基であり、
いずれも平均値でbは0から3.4であり、cは0.1から3.5であり、且つbおよびcの和は1.0から3.5である上記(1)又は(2)に記載のポルフィラジン色素又はその塩、
(5)
Eがエチレン基またはプロピレン基である上記(4)に記載のポルフィラジン色素又はその塩、
(6)破線で表される環A、B、C及びDの4つの環のうち、平均値で0.5乃至3.0個が、2位及び3位または、3位及び4位で縮環したピリジン環であり、且つ、残りのうち、1.0乃至3.5個がベンゼン環であり、
EがC2-C4アルキレンであり、
X及びYはそれぞれ独立して、カルボキシ基を1乃至3有するアニリノ基であり、
いずれも平均値でbが0から3.4であり、cが0.1から3.5であり、且つbおよびcの和は1.0から3.5である上記(1)に記載のポルフィラジン色素又はその塩、
(7)下記式(2)で表される上記(1)または(2)に記載のポルフィラジン色素又はその塩
E、X、Y、bおよびcは上記(1)に記載のものと同じ意味を表す。]、
(8)下記式(5)で表される化合物と、下記式(4)で表される有機アミンとをアンモニア存在下で反応させて得られる上記(7)に記載のポルフィラジン色素またはその塩
(9)色素成分として上記(1)から(8)のいずれか一項に記載のポルフィラジン色素を含有することを特徴とするインク組成物、
(10)水溶性有機溶剤をさらに含有する上記(9)に記載のインク組成物、
(11)インクジェット記録用である上記(9)または(10)に記載のインク組成物、
(12)上記(9)から(11)のいずれか一項に記載のインクのインク滴を記録信号に応じて吐出させて被記録材に記録を行うことを特徴とするインクジェット記録方法、
(13)被記録材が情報伝達用シートである上記(12)に記載のインクジェット記録方法、
(14)情報伝達用シートが表面処理されたシートであって、支持体上に白色無機顔料粒子を含有するインク受像層を有するシートである上記(13)に記載のインクジェット記録方法、
(15)上記(9)から(11)のいずれか一項に記載のインク組成物を含有する容器、
(16)上記(15)に記載の容器を装着したインクジェットプリンター、
(17)上記(1)~(8)に記載のポルフィラジン色素、又は上記(9)から(11)のいずれか一項に記載のインク組成物で着色された着色体、
に関する。
更に本発明のインク組成物は、従来の染料インクと比較して普通紙上での耐水性が極めて向上している。また、該インク組成物で、写真画質用インクジェット専用紙やフィルムのような多孔性白色無機物を表面に塗工した被記録材に記録しても各種堅牢性、すなわち耐水性、耐湿性、耐ガス性、および耐光性が良好である。従って、写真調の記録画像の長期保存安定性にも優れている。これらの特徴から該インク組成物は、記録メディアを選ばないことが特徴の一つであるインクジェット印刷に非常に適している。このように、上記式(1)で表される水溶性ポルフィラジン色素はインク用、特にインクジェット記録用インクのシアン色素として極めて有用である。
また、本明細書において上付き文字の「RTM」は登録商標を示す。
環A乃至Dにおけるベンゼン環又は含窒素複素芳香環の個数は、前記式(1)で表される色素におけるベンゼン環又は含窒素複素芳香環の個数の平均値で表される。即ち、単純化して説明すると例えば、3.5個がベンゼン環で、0.5個が含窒素複素芳香環である式(1)で表される色素という場合、平均で、全色素分子の2分の1がA~Dの全てがベンゼン環の化合物であり、残りの2分の1がA~Dのうち一つが含窒素複素芳香環の化合物ということであり、また、例えば、2.5個がベンゼン環で、1.5個が含窒素複素芳香環である式(1)で表される色素という場合、平均で、全色素分子の2分の1がA~Dの中、2つがベンゼン環の化合物であり、残りの2分の1がA~Dのうち一つが含窒素複素芳香環の化合物であるということである。従って、含窒素複素芳香環の数が、1以下の場合には、前記式(1)で表される色素は、環A乃至Dの少なくとも1つが該含窒素複素芳香環である色素と、環A乃至Dがいずれもベンゼン環である色素の両者を含むものである。なお本発明のポルフィラジン色素は、通常、上記のような2成分の単純な混合物ではないが、上記の値はそれらの混合物の平均値ということである。
該含窒素複素芳香環としては、窒素原子を1~2個含む含窒素複素芳香6員環が好ましく、例えば、ピリジン環、ピラジン環、ピリミジン環、ピリダジン環があげられる。これらの中でもピリジン環又はピラジン環が好ましく、ピリジン環がより好ましい。
該環A、B、C及びDの4つの環のうち、好ましい具体的な含窒素複素芳香環の数としては、平均値で通常0.5乃至3.0個、好ましくは0.5乃至2.5個、より好ましくは0.5乃至2.0個であり、残りがベンゼン環である。すなわち、この場合のベンゼン環の具体的な数は、平均値で通常1.0乃至3.5個であり、好ましくは1.5乃至3.5個、より好ましくは2.0乃至3.5個である。
該含窒素複素芳香環の縮合位置は、2つの連続した炭素原子が複数存在する場合、そのいずれの位置でもよい。例えば、ピリジン環の場合には、2位及び3位または、3位及び4位が挙げられ、2位及び3位で縮環するのが好ましい。ピラジン環の場合には2位及び3位である。
該含窒素複素芳香環の個数が増えるにしたがって、水及び有機溶剤等への溶解性は低下する傾向にある。このため、含窒素複素芳香環の個数は耐水性と溶解性を考慮しながら、適宜調節し、バランスの良い比率を選択すれば良い。
本発明化合物の場合、含窒素複素芳香環の数が、平均値で、該環A、B、C及びDの4つの環のうち、上記範囲の時好ましいが、更に好ましい場合として、含窒素複素芳香環の数が、平均値で、0.50~2.0個、又は、0.50~1.5個、場合によって、0.70~1.5個である場合を挙げることができ、この場合残りがベンゼン環である。
式(2)において、Z1からZ8はそれぞれ独立して窒素原子または炭素原子を表し(炭素原子の場合、該炭素原子は水素原子1つを有する)、且つ、Z1とZ2、Z3とZ4、Z5とZ6及びZ7とZ8の4つ組み合わせのうち、平均値で、少なくとも1.0個は炭素原子同士の組合せ(即ち、環がベンゼン環となる組合せ)、残りの組合せの少なくとも0.5個は環が含窒素芳香環となる組合せ、即ち、窒素原子と炭素原子の組合せ又は窒素原子同士の組合わせである。
従って、ここでの4つの組合せについての平均値は、前記の式(1)の環A乃至Dにおける含窒素複素芳香環及びベンゼン環の個数の平均値と同様な意味であり、好ましい範囲等も全く同じである。
より具体的には、含窒素複素芳香環となる組合せの好ましい数としては、平均値で通常0.5乃至3.0個、好ましくは0.5乃至2.5個、より好ましくは0.5乃至2.0個であり、残りがベンゼン環となる組合せである。また、更に好ましい場合として、含窒素複素芳香環となる組合せの数が、平均値で、0.50~2.0個、又は、0.50~1.5個、場合によって、0.70~1.5個である場合を挙げることができ、この場合残りがベンゼン環である。
また、式(2)におけるE、X、Y、bおよびcは、それぞれ上記式(1)の場合と、好ましいものも含めて同じである。なお、Z1からZ8のいずれかが炭素原子の場合には、該炭素原子は水素原子を一つ有する。
アルカリ土類金属塩のアルカリ土類金属としては、例えばカルシウム、マグネシウム等があげられる。
有機陽イオンの塩としては、有機アミンのカチオン、すなわち有機アミンのオニウム塩が挙げられる。該有機アミンとしては、例えばメチルアミン、エチルアミン等の炭素数1から3の低級アルキルアミン類、及び、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、モノイソプロパノールアミン、ジイソプロパノールアミン、トリイソプロパノールアミン等のモノ、ジまたはトリ(炭素数1から4の低級アルカノール)アミン類があげられる。
また他の塩としてアンモニウム塩があげられる。
上記のうち、好ましい塩としてはナトリウム塩、カリウム塩、リチウム塩等のアルカリ金属塩;モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、モノイソプロパノールアミン、ジイソプロパノールアミン、トリイソプロパノールアミン等のモノ、ジまたはトリ(炭素数1から4の低級アルカノール)アミンのオニウム塩;及びアンモニウム塩があげられる。
なお、本発明の式(1)で表される色素を合成する際には後記するように主成分以外に位置異性体及びその他の副生物が混入するが、そのまま使用しても、本発明において特に問題は生じない。
含窒素複素芳香環ジカルボン酸誘導体としては、隣接する2つの位置にそれぞれカルボキシル基又はカルボキシル基から誘導される反応性の基(酸アミド基、イミド基、酸無水物基、カルボニトリル基など)を有する6員環の含窒素複素芳香環ジカルボン酸誘導体が挙げられ、具体的には6員含窒素複素芳香環ジカルボン酸及びそれから誘導される酸アミド、酸イミド、酸無水物又はカルボニトリル等が挙げられる。より具体的には、キノリン酸、3,4-ピリジンジカルボン酸、2,3-ピラジンジカルボン酸等のジカルボン酸化合物;無水キノリン酸、3,4-ピリジンジカルボン酸無水物、2,3-ピラジンジカルボン酸無水物等の酸無水物化合物;ピリジン-2,3-ジカルボキシアミド等のジカルボキシアミド化合物、ピラジン-2,3-ジカルボン酸モノアミド等のジカルボン酸モノアミド化合物;キノリン酸イミド等の酸イミド化合物;及び、ピリジン-2,3-ジカルボニトリル、ピラジン-2,3-ジカルボニトリル等のジカルボニトリル化合物があげられる。またフタル酸誘導体の具体例としては、フタル酸、無水フタル酸、フタルアミド、フタラミックアシッド、フタルイミド、フタロニトリル、1,3-ジイミノイソインドリン、及び2-シアノベンズアミド等があげられる。
ニトリル法とはピリジン-2,3-ジカルボニトリル、ピラジン-2,3-ジカルボニトリル、フタロニトリル等のジカルボニトリル化合物を原料とする方法である。
一方、ワイラー法はフタル酸、キノリン酸、3,4-ピリジンジカルボン酸、2,3-ピラジンジカルボン酸等のジカルボン酸化合物;無水フタル酸、無水キノリン酸、3,4-ピリジンジカルボン酸無水物、2,3-ピラジンジカルボン酸無水物等の酸無水物化合物;フタル酸アミド、ピリジン-2,3-ジカルボキシアミド等のジカルボキシアミド化合物;フタラミック酸、ピラジン-2,3-ジカルボン酸モノアミド等のジカルボン酸モノアミド化合物;及び、フタル酸イミド、キノリン酸イミド等の酸イミド化合物;等を原料として用いる。またワイラー法では尿素の添加が必須であり、尿素の使用量は含窒素複素芳香環ジカルボン酸誘導体とフタル酸誘導体の総計1モルに対し5~100倍モル量である。
また、ワイラー法における溶媒としては沸点150℃以上、より好ましくは180℃以上の非プロトン性有機溶媒が用いられる。ワイラー法における溶媒の具体例としては、トリクロロベンゼン、クロロナフタレン、ニトロベンゼン、キノリン、スルホラン及び尿素等が挙げられる。溶媒の使用量は含窒素複素芳香環ジカルボン酸誘導体とフタル酸誘導体の総計の1~100質量倍である。なお、尿素は有機溶媒ではなく、室温では固体であるが、その融点は132℃であるため、これ以上の温度で反応させる場合には、上記の各反応における溶媒として好ましく使用することができる。
環A乃至Dのうち2つがピリジン環以外の含窒素複素芳香環、例えばピラジン環等の場合にも、上記キノリン酸の代わりに、2,3-ピラジンジカルボン酸等の対応する該含窒素複素芳香環のジカルボン酸誘導体を用いて、上記に準じて合成することにより、環A乃至Dのうち2つがピラジン環等のピリジン環以外の含窒素複素芳香環であり、残り2つがベンゼン環である化合物を得ることができる。また、環A乃至Dのうち含窒素複素芳香環が平均値で0.5個乃至3.0個であり残りがベンゼン環である前記式(6)の化合物等のその比率の異なる化合物についても、目的化合物の含窒素複素芳香環とベンゼン環の比率に応じて、含窒素複素芳香環ジカルボン酸誘導体とフタル酸誘導体の使用割合を適宜変えることにより、上記と同様の合成法で該化合物を得ることができる。
従って、式(3)の化合物におけるSO2Clの数(n)は、式(3)の化合物の環A乃至Dにおけるベンゼン環の数に応じて、平均値で1.0~3.5である。式(3)におけるnは、好ましくは1.5~3.5であり、より好ましくは2.0~3.5である。式(5)におけるnも、式(3)の場合と同様で、そのnの数は平均値で1.0~3.5、好ましくは1.5~3.5、より好ましくは2.0~3.5である。
前記式(3)で表される化合物の他の合成例としては、予めスルホ基を有するスルホフタル酸とキノリン酸とを用いて縮合閉環させる事により、下記式(10)で表されるスルホ基を有する化合物を合成し、その後スルホ基をクロロスルホ基へ変換することにより目的の式(3)で表される化合物を得る事もできる。式(5)の化合物についても、対応する原料化合物を使用することにより全く同様にして合成することができる。
前記式(10)で表されるスルホ置換銅ポルフィラジン色素におけるスルホ基からクロロスルホ基への変換は、上記と同様に該化合物に上記のクロロ化剤を反応させることにより、行うことができる。該クロロ化反応に用いられる反応溶媒としては、硫酸、発煙硫酸、クロロスルホン酸、ベンゼン、トルエン、ニトロベンゼン、クロロベンゼン、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド等が挙げられるが、これらに限定されるものではない。
本発明のポルフィラジン色素におけるb及びcの値は、上記の通り、合成反応時における式(4)で表される有機アミンの使用量によって調整することができる。例えば、式(1)においてbが1.0であり、cが1.5であり、b及びcの総和が2.5である化合物を得るためには、式(3)においてnが2.5である化合物1モルに対し、式(4)で表される有機アミンを1.5モル又はその小過剰を使用して上記合成反応を行えばよい。式(3)で表される化合物と式(4)で表される有機アミンとの合成反応によって得られる生成物は、実質的には、様々なb及びcの値を有する化合物の混合物である。従って、式(1)及び式(2)におけるb及びcの値はこれら混合物におけるb及びcの平均値である。
しかしながら、通常、反応生成物の分析に使用する質量分析法においては、無置換スルファモイル基とスルホン酸基とを識別することは困難である。従って本発明においては、式(4)で表される有機アミンと反応したもの以外の式(3)又は式(5)におけるクロロスルホニル基については、全て無置換スルファモイル基へと変換されたものとして表記する。
上記Lで表される2価の連結基としては-SO2-、-SO2-NH-SO2-などがあり、3量体の場合にはこれら2つのLが組み合わされた副生成物が形成される場合も有る。
こうして得られた本発明のポルフィラジン色素は、必要に応じて酸析又は塩析後、濾過等により分離することが出来る。塩析を行う場合には例えば酸性~アルカリ性、好ましくはpH1~11の範囲で行うことが好ましい。塩析の際の温度は特に限定されないが、通常40~80℃、好ましくは50~70℃である。より具体的には、本発明のポルフィラジン色素を含む反応液を上記温度に加熱後、塩化ナトリウム又は塩化アンモニウム等を加えてpHを上記範囲に調整して、塩析するのが好ましい。
環A乃至Dのうち0.5個乃至3.0個、より好ましくは0.5個乃至2.5個、さらに好ましくは0.5個乃至2.0個がピリジン環又はピラジン環(より好ましくはピリジン環)であって、残りの1.0個乃至3.5個、より好ましくは1.5個乃至3.5個、更に好ましくは2.0個乃至3.5個がベンゼン環であり;
EがC2~C4アルキレン基、より好ましくはエチレン基又はプロピレン基であり;
X及びYが独立してカルボキシ基を1乃至3個有するアニリノ基、より好ましくはカルボキシ基を1又は2個有するアニリノ基、さらに好ましくは3-カルボキシアニリノ、4-カルボキシアニリノ又は3,5-ジカルボキシアニリノ、特に好ましくは3-カルボキシアニリノであり;
いずれも平均値でbが0~3.4、且つ、cが0.1~3.5、好ましくは、bが0.5~3.0、且つ、cは0.5~2.5であり;
b及びcの和が1.5~3.5、より好ましくは2.0~3.5、さらに好ましくは2.5~3.5;である場合である。
これらの中のより好ましいものと他のものとの組み合わせはより好ましく、より好ましいもの同士の2種又は3種の組み合わせはさらに好ましい。
例えば、(i)式(1)における破線で表される環A、B、C及びDの4つの環、又は式(2)のZ1とZ2、Z3とZ4、Z5とZ6及びZ7とZ8を含む4つの環のうち、平均値で、0.5乃至3.0個がピリジン環またはピラジン環であり、且つ、残りのうち、1.0乃至3.5個がベンゼン環であり、
EがC2-C4アルキレン基であり、
X及びYはそれぞれ独立して、カルボキシ基を1乃至3有するアニリノ基であり、
いずれも平均値で、bは0から3.4、場合によって0から3.2であり、cは0.1から3.5、場合によって0.1から3.3であり、且つbおよびcの和は1.0から3.5、場合によって2.5から3.3であるポルフィラジン色素、
(ii)上記(i)において、4つの環のうち、平均値で、0.50~2.0個、又は、0.50~1.5個、場合によって、0.70~1.5個がピリジン環またはピラジン環であり、残りがベンゼン環であるポルフィラジン色素、
(iii)上記の(i)又は(ii)において、X及びYがそれぞれ独立に、3-又は4-カルボキシアニリノ、又は3,5-ジカルボキシアニリノであるポルフィラジン色素、
を挙げることができる。
有機ハロゲン系化合物としては、例えばペンタクロロフェノールナトリウムが挙げられる。
ピリジンオキシド系化合物としては、例えば2-ピリジンチオール-1-オキサイドナトリウムが挙げられる。
イソチアゾリン系化合物としては、例えば1,2-ベンズイソチアゾリン-3-オン、2-n-オクチル-4-イソチアゾリン-3-オン、5-クロロ-2-メチル-4-イソチアゾリン-3-オン、5-クロロ-2-メチル-4-イソチアゾリン-3-オンマグネシウムクロライド、5-クロロ-2-メチル-4-イソチアゾリン-3-オンカルシウムクロライド、2-メチル-4-イソチアゾリン-3-オンカルシウムクロライド等が挙げられる。
その他の防腐防黴剤として酢酸ソーダ、ソルビン酸ソーダ、安息香酸ナトリウム等(例えば、アベシア社製 商品名プロクセルRTMGXL(S)、プロクセルRTMXL-2(S)等)があげられる。
防錆剤としては、例えば、酸性亜硫酸塩、チオ硫酸ナトリウム、チオグリコール酸アンモニウム、ジイソプロピルアンモニウムナイトライト、四硝酸ペンタエリスリトール、ジシクロヘキシルアンモニウムナイトライトなどがあげられる。
アニオン界面活性剤としてはアルキルスルホカルボン酸塩、α-オレフィンスルホン酸塩、ポリオキシエチレンアルキルエーテル酢酸塩、N-アシルアミノ酸又はその塩、N-アシルメチルタウリン塩、アルキル硫酸塩ポリオキシアルキルエーテル硫酸塩、アルキル硫酸塩ポリオキシエチレンアルキルエーテル燐酸塩、ロジン酸石鹸、ヒマシ油硫酸エステル塩、ラウリルアルコール硫酸エステル塩、アルキルフェノール型燐酸エステル、アルキル型燐酸エステル、アルキルアリールスルホン酸塩、ジエチルスルホ琥珀酸塩、ジエチルヘキルシルスルホ琥珀酸塩、ジオクチルスルホ琥珀酸塩などが挙げられる。
カチオン界面活性剤としては2-ビニルピリジン誘導体、ポリ4-ビニルピリジン誘導体などがある。
両性界面活性剤としてはラウリルジメチルアミノ酢酸ベタイン、2-アルキル-N-カルボキシメチル-N-ヒドロキシエチルイミダゾリニウムベタイン、ヤシ油脂肪酸アミドプロピルジメチルアミノ酢酸ベタイン、ポリオクチルポリアミノエチルグリシン、イミダゾリン誘導体などがある。
ノニオン界面活性剤としては、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンドデシルフェニルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンアルキルエーテル等のエーテル系;ポリオキシエチレンオレイン酸エステル、ポリオキシエチレンジステアリン酸エステル、ソルビタンラウレート、ソルビタンモノステアレート、ソルビタンモノオレエート、ソルビタンセスキオレエート、ポリオキシエチレンモノオレエート、ポリオキシエチレンステアレートなどのエステル系;2,4,7,9-テトラメチル-5-デシン-4,7-ジオール、3,6-ジメチル-4-オクチン-3,6-ジオール、3,5-ジメチル-1-ヘキシン-3-オールなどのアセチレングリコール(アルコール)系のもの等が挙げられる。他の具体例として、例えば、サーフィノールRTM104、82、465、オルフィンSTG(以上、日信化学工業株式会社製)等が挙げられる。
本発明のインクジェット記録方法で、被記録材に記録するには、例えば上記のインクを含有する容器(インクタンク等とも呼称される)をインクジェットプリンタの所定位置にセットし、通常の方法で、被記録材に記録すればよい。インクジェットプリンタとしては、例えば機械的振動を利用したピエゾ方式のプリンタや加熱により生ずる泡を利用したバブルジェットRTM方式のプリンタ等があげられる。
普通紙は、特にインク受容層を設けていない紙のことを指し、用途によってさまざまなものが数多く市販されている。市販されている普通紙の一例を挙げると、インクジェット用としては、セイコーエプソン株式会社製 両面上質普通紙;キヤノン株式会社製 カラー普通紙;Hewlett Packard社製 Multipurpose Paper、All-in-one Printing Paper;などがある。この他、特に用途をインクジェット印刷に限定しないPPC用紙なども普通紙である。
本発明のインク組成物は、上記のような普通紙上での耐水性が特に優れており、この理由から特に普通紙に好適に用いられる。加えて、光、オゾン、湿度や摩擦などに対する耐性にも優れる。インクジェット印刷用にインク受容層を設けているインクジェット専用紙、専用フィルム、光沢紙または光沢フィルムなどでの耐水性にも優れ、またそれらの情報伝達用シート上での耐光性、耐オゾン性、耐湿性及び耐擦性などにも優れる。
なお合成した本発明のポルフィラジン色素は、いずれも水に対して100g/L以上の溶解度を示した。
(1)前記式(6)において、環A乃至Dのうち、平均値で1.5個がピリジン環、2.5個がベンゼン環である化合物の合成。
四つ口フラスコに、スルホラン250部、フタルイミド18.4部、キノリン酸12.5部、尿素72.0部、塩化銅(II)・2水和物(純度97.0%)8.8部、モリブデン酸アンモニウム1.0部を加え、液温を200℃まで上げ、同温度で5時間保持し、反応を行った。反応終了後、反応液を65℃まで冷却し、そこにメタノール200部を加え、析出した固体を濾過分離した。得られた固体をメタノール150部、続いて温水200部で洗浄することにより、ウェットケーキ72.2部を得た。得られたウェットケーキの全量を5%塩酸500部中に加えた後、液温を60℃に上げ、同温度で1時間保持した。析出固体を室温下において濾過分離し、水200部で洗浄することにより、ウェットケーキを得た。得られたウェットケーキの全量を10%アンモニア水500部中に加え、該液を60℃で1時間保持した。析出した固体を濾過分離し、得られた固体を水300部、メタノール100部で順次洗浄し、ウェットケーキ33.6部を得た。得られたウェットケーキを80℃で乾燥することにより、目的とする化合物19.8部を青色固体として得た。
λmax:663.5nm(ピリジン中)
クロロスルホン酸46.2部中に、60℃以下の温度を保ちながら実施例1(1)で得られた化合物5.8部を徐々に加えた後、液温を140℃まで上げ、この温度で4時間反応を行った。反応液を70℃まで冷却し、塩化チオニル17.9部を反応液に30分間かけて滴下し、同温度で3時間反応を行った。反応液を30℃以下に冷却し、氷水800部中にゆっくりと注いだ。析出した固体を濾過分離し、冷水200部で洗浄することにより、目的化合物のウェットケーキ40.0部を得た。
λmax:610.5nm(水溶液中)
(1)下記式(14)[式(4)におけるX及びYが4-カルボキシアニリノ、Eがエチレン]で表される化合物の合成。
λmax:610.5nm(水溶液中)
(1)下記式(16)[式(4)におけるX及びYが3,5-ジカルボキシアニリノ、Eがエチレン]で表される化合物の合成。
λmax:603.5nm(水溶液中)
(1)前記式(6)における環A乃至Dのうち、平均値で1.0個がピリジン環、3.0個がベンゼン環で表される化合物の合成。
四つ口フラスコに、スルホラン250部、フタルイミド22.1部、キノリン酸8.36部、尿素72.0部、塩化銅(II)・2水和物(純度97.0%)8.8部、モリブデン酸アンモニウム1.0部を加えた後、液温を200℃まで上げ、反応液を同温度で5時間保持した。反応終了後、反応液を65℃まで冷却し、そこにメタノール200部を加え、析出した固体を濾過分離した。得られた固体をメタノール150部、温水200部で順次洗浄することにより、ウェットケーキ74.2部を得た。得られたウェットケーキの全量を5%塩酸500部中に加えた後、液温を60℃に上げ、該反応液を同温度で1時間保持した。析出した固体を濾過分離し、水200部で洗浄することにより、ウェットケーキを得た。得られたウェットケーキの全量を10%アンモニア水500部中に加えた後、該反応液を60℃で1時間保持した。析出した固体を濾過分離し、水300部、メタノール100部で順次洗浄することにより、ウェットケーキ36.6部を得た。得られたウェットケーキを80℃で乾燥することにより、目的とする化合物21.8部を青色固体として得た。
λmax:655.0nm(ピリジン中)
クロロスルホン酸46.2部中に、液温を60℃以下に保持しながら、本実施例の(1)で得られた化合物5.8部を徐々に加えた後、液温を140℃まで上げて4時間反応を行った。反応液を70℃まで冷却し、塩化チオニル17.9部を反応液に30分間かけて滴下し、同温度で3時間反応を行った。反応液を30℃以下に冷却し、氷水800部中にゆっくりと注いだ。析出した固体を濾過分離し、冷水200部で洗浄することにより、目的化合物のウェットケーキ41.0部を得た。
氷水100部中に、本実施例の(2)で得られたウェットケーキ41.0部を加え、この懸濁液を5℃以下で撹拌した。10分後、液温を10℃以下を保持しながら、28%アンモニア水2.5部及び水60部中に実施例1(3)と同様にして得られた前記式(12)で表される化合物5.2部を溶解させた液を加えた後、更に、そこに28%アンモニア水を添加し、pHを9.0に調整した。適宜同アンモニア水を追加して、同pHを保持しながら、1時間かけて液温を20℃まで上げ、同温度で反応液を8時間保持した。この時の反応液の総量は230部であった。反応液の液温を50℃に上げ、濃塩酸で20分かけてpH2.0に調整した後、析出した固体を濾過分離し、水200部で洗浄して、ウエットケーキ55.0部を得た。得られたウェットケーキを乾燥することにより、目的とする前記式(13)で表される本発明のポルフィラジン色素(bが2.08、cが0.92の色素)の遊離酸を青色粉末として10.8部得た。
λmax:611.0nm(水溶液中)
(1)前記式(6)における環A乃至Dのうち、平均値で0.75個がピリジン環、3.25個がベンゼン環で表される化合物の合成。
四つ口フラスコに、スルホラン250部、フタルイミド23.9部、キノリン酸6.27部、尿素72.0部、塩化銅(II)・2水和物(純度97.0%)8.8部、モリブデン酸アンモニウム1.0部を加えた後、液温を200℃まで上げ、反応液を同温度で5時間反応した。反応終了後、液温を65℃まで冷却し、反応液にメタノール200部を加え、析出した固体を濾過分離した。得られた固体をメタノール150部、温水200部で順次洗浄することにより、ウェットケーキ78.3部を得た。得られたウェットケーキの全量を5%塩酸500部中に加えた後、液温を60℃に上げ、同温度で反応液を1時間保持した。析出した固体を濾過分離し、水200部で洗浄して、ウェットケーキを得た。得られたウェットケーキの全量を10%アンモニア水500部中に加えた後、液温を60℃に上げ、同温度で反応液を1時間保持した。析出した固体を濾過分離した後、水300部、メタノール100部で順次洗浄することにより、ウェットケーキ39.4部を得た。得られたウェットケーキを80℃で乾燥することにより、目的化合物24.3部を青色固体として得た。
クロロスルホン酸46.2部中に、液温を60℃以下に保持しながら、本実施例の(1)で得られた化合物5.8部を徐々に加えた。その後、液温を140℃まで上げて4時間反応を行った。反応液を70℃まで冷却し、塩化チオニル17.9部を反応液に30分間かけて滴下し、同温度で3時間反応を行った。反応液を30℃以下に冷却し、氷水800部中にゆっくりと注いだ。析出した固体を濾過分離し、冷水200部で洗浄することにより、目的化合物43.3部を得た。
氷水100部中に本実施例の(2)で得られた化合物のウェットケーキ43.3部を加え、この懸濁液を5℃以下で撹拌した。10分後、液温を10℃以下に保持しながら、28%アンモニア水2.5部及び水60部中に実施例1(3)と同様にして得られた前記式(12)で表される化合物4.1部を溶解させた液を加えた後、更に、そこに28%アンモニア水を添加し、pHを9.0に調整した。適宜同アンモニア水を追加して、同pHを保持しながら、1時間かけて液温を20℃まで上げ、同温度で8時間保持し、反応を行った。この時の反応液の総量は240部であった。反応液の液温を50℃に上げ、濃塩酸で、20分かけてpH2.0に調整した。析出した固体を濾過分離した後、水200部で洗浄して、ウエットケーキ92.0部を得た。得られたウェットケーキを乾燥することにより、目的とする前記式(13)で表される本発明のポルフィラジン色素(bが2.29、cが0.96の色素)の遊離酸を青色粉末として11.9部得た。
λmax:611.5nm(水溶液中)
(A)インクの調製
実施例6~10
色素として上記実施例1で得られた本発明のポルフィラジン色素を用い、下記表2に示した組成比で各成分を混合して本発明のインク組成物とした後、0.45μmのメンブランフィルターで濾過する事により夾雑物を除き、評価試験用のインクジェット記録用インクを調製した。このインクの調製を実施例6とする。尚、水はイオン交換水を使用し、インク組成物のpHがおよそ9.5、総量が100部になるようにアンモニア水溶液及び水を加えた。
また実施例1で得られた本発明のポルフィラジン色素の代わりに、実施例2乃至5で得られた色素を用いる以外は実施例6と同様にしてインクを調製した。このインクの調製を、それぞれ実施例7乃至10とする。
実施例1で得られたポルフィラジン色素 5.0部
グリセリン 5.0部
尿素 5.0部
N-メチル-2-ピロリドン 4.0部
イソプロピルアルコール 3.0部
ブチルカルビトール 2.0部
商品名サーフィノールRTM104PG50(注) 0.1部
アンモニア水+水 75.9部
計 100.0部
(注)アセチレングリコ-ル系ノニオン界面活性剤、日信化学工業株式会社製
色素として実施例1で得られた本発明のポルフィラジン色素のかわりに、下記式(18)で表される色素(C.I.Direct Blue 86)を用いる以外は実施例1と同様にして、比較例1のインクを調製した。
なお、該色素中のスルホン酸基はフタロシアニンの3位に置換しているものの混合物であり、下記式(18)は考えられる構造式のうちの一つを示した。なお、この色素はナトリウム塩であることが知られている。
比較例1で用いた色素のナトリウム塩を、常法に従いアンモニウム塩へと交換した。色素として実施例1で得られた本発明のポルフィラジン色素の代わりに、上記塩の交換により得られた比較例1の色素のアンモニウム塩を用いる以外は実施例1と同様にして、比較例2のインクを調製した。
色素として実施例1で得られた本発明のポルフィラジン色素のかわりに、下記式(19)で表される特許文献15の実施例3(2)に記載の色素を用いる以外は実施例1と同様にして、比較例3のインクを調製した。
なお、下記式(19)中、A~Dの4個の6員芳香環のうち、1.5個が2位及び3位で縮環したピリジン環で、残り2.5個がベンゼン環である。
色素として実施例1で得られた本発明のポルフィラジン色素のかわりに、下記式(20)で表される特許文献15の実施例5に記載の色素を用いる以外は実施例1と同様にして比較例4のインクを調製した。
なお、下記式(20)中、A~Dの4個の6員芳香環のうち、1.5個が2位及び3位で縮環したピリジン環で、残り2.5個がベンゼン環である。
インクジェットプリンタ(キヤノン株式会社製、商品名:PIXUSRTMip4100)を用いて、実施例6乃至10及び比較例1乃至4で調製したインクを使用し、表3に示す3種類の普通紙にインクジェット記録を行った。インクジェット記録の際、チェック柄のパターン(濃度100%と0%の1.5mm角を有する正方形を交互に組み合わせたパターン)を作成し、コントラストの高いシアン-ホワイトのチェック柄の印字物を得た。また、反射濃度が数段階の階調が得られるように画像パターンも作成し、シアン色の濃度階調のあるグラデーションの印字物を得た。
普通紙1
キヤノン株式会社製:
LBP PAPER LS-500
普通紙2
Hewlett Packard社製:
Multipurpose Paper
普通紙3
Hewlett Packard社製:
All-in-One Printing Paper
耐水性試験1の目視判断を行う際には、上記インクジェットプリントのチェック柄の印字物を用いた。
耐水性試験2の色素残存率測定は、上記インクジェットプリントのグラデーションの印字物を用い、試験前の印字物の反射濃度D値が1に最も近い部分について反射濃度の測定を行った。また、反射濃度は測色システム(SpectroEyeRTM、GretagMacbeth社製)を用いて測定した。
(C)耐水性試験1
印刷後24時間乾燥を行ったチェック柄の印字物を、イオン交換水中に1時間浸漬した。印字物を水から取出した後、乾燥し、パターンの着色部分の色落ち具合とホワイト部分の着色具合とを目視で評価し、下記の基準で3段階に評価した。結果を表4に示した。
評価基準
色落ちがやや見られる ・・・・・・○
色落ちは見られるが着色の残存がある・・・・・・△
全て色落ちする ・・・・・・×
印刷後24時間乾燥を行ったグラデーションの印字物に対して、イオン交換水中に1時間浸漬した。印字物を水から取出した後、乾燥し、反射濃度を前記の測色システムを用いて測色した。測定後、色素残存率を下記式で計算して求め、以下の基準で3段階で評価した。結果を表5に示す。
色素残存率=(試験後の反射濃度/試験前の反射濃度)×100(%)
評価基準
色素残存率が80%以上・・・・・・・・○
色素残存率が50%以上80%未満・・・△
色素残存率が50%未満・・・・・・・・×
(普通紙1)(普通紙2)(普通紙3)
実施例6 △ ○ ○
実施例7 △ ○ ○
実施例8 △ ○ ○
実施例9 △ ○ ○
実施例10 △ ○ ○
比較例1 × × ×
比較例2 × × ×
比較例3 × × ×
比較例4 × × ×
(普通紙1)(普通紙2)(普通紙3)
実施例6 △ ○ ○
実施例7 △ ○ ○
実施例8 △ ○ ○
実施例9 △ ○ ○
実施例10 △ ○ ○
比較例1 × × ×
比較例2 × × ×
比較例3 × × ×
比較例4 × × ×
これに対して各実施例のインクは、耐水性試験1及び2のいずれの場合においても、良好な結果が得られ、普通紙での耐水性が各比較例と比べて極めて高いことがわかる。
Claims (17)
- 含窒素複素芳香環が、ピリジン環またはピラジン環である請求項1に記載のポルフィラジン色素又はその塩。
- 破線で表される環A、B、C及びDの4つの環のうち、平均値で、0.5乃至3.0個がピリジン環またはピラジン環であり、且つ、残りのうち、1.0乃至3.5個がベンゼン環であり、
EがC2-C4アルキレン基であり、
X及びYはそれぞれ独立して、カルボキシ基を1乃至3有するアニリノ基であり、
いずれも平均値で、bは0から3.4であり、cは0.1から3.5であり、且つbおよびcの和は1.0から3.5である請求項1に記載のポルフィラジン色素又はその塩。 - Eがエチレン基またはプロピレン基である請求項4に記載のポルフィラジン色素又はその塩。
- 破線で表される環A、B、C及びDの4つの環のうち、平均値で、0.5乃至3.0個が、2位及び3位または、3位及び4位で縮環したピリジン環であり、且つ、残りのうち、1.0乃至3.5個がベンゼン環であり、
EがC2-C4アルキレンであり、
X及びYはそれぞれ独立して、カルボキシ基を1乃至3有するアニリノ基であり、
いずれも平均値でbが0から3.4であり、cが0.1から3.5であり、且つbおよびcの和は1.0から3.5である請求項1に記載のポルフィラジン色素又はその塩。 - 色素成分として請求項1、3及び6のいずれか一項に記載のポルフィラジン色素を含有することを特徴とするインク組成物。
- 水溶性有機溶剤をさらに含有する請求項9に記載のインク組成物。
- インクジェット記録用である請求項10に記載のインク組成物。
- 請求項1に記載のポルフィラジン色素を含有するインク組成物のインク滴を記録信号に応じて吐出させて被記録材に記録を行うことを特徴とするインクジェット記録方法。
- 被記録材が情報伝達用シートである請求項12に記載のインクジェット記録方法。
- 情報伝達用シートが表面処理されたシートであって、支持体上に白色無機顔料粒子を含有するインク受像層を有するシートである請求項13に記載のインクジェット記録方法。
- 請求項9に記載のインク組成物を含有する容器。
- 請求項15に記載の容器を装着したインクジェットプリンター。
- 請求項1に記載のポルフィラジン色素、又は請求項9に記載のインク組成物で着色された着色体。
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- 2008-12-25 US US12/810,376 patent/US7981204B2/en not_active Expired - Fee Related
- 2008-12-25 WO PCT/JP2008/003947 patent/WO2009084195A1/ja active Application Filing
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Cited By (13)
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US7981204B2 (en) | 2007-12-28 | 2011-07-19 | Nippon Kayaku Kabushiki Kaisha | Porphyrazine coloring matter and ink composition containing the same |
JP5458010B2 (ja) * | 2008-06-30 | 2014-04-02 | 日本化薬株式会社 | ポルフィラジン色素、インク組成物及び着色体 |
US8394186B2 (en) | 2008-06-30 | 2013-03-12 | Nippon Kayaku Kabushiki Kaisha | Porphyrazine coloring matter, ink composition and colored product |
WO2010001559A1 (ja) * | 2008-06-30 | 2010-01-07 | 日本化薬株式会社 | ポルフィラジン色素、インク組成物及び着色体 |
WO2010038051A2 (en) * | 2008-10-01 | 2010-04-08 | Fujifilm Imaging Colorants Limited | Phthalocyanines and their use in ink-jet printing |
WO2010038051A3 (en) * | 2008-10-01 | 2010-06-24 | Fujifilm Imaging Colorants Limited | Phthalocyanines and their use in ink-jet printing |
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GB2475993B (en) * | 2008-10-01 | 2012-06-27 | Fujifilm Imaging Colorants Ltd | Phthalocyanines and their use in ink-jet printing |
WO2010073603A1 (ja) * | 2008-12-25 | 2010-07-01 | 日本化薬株式会社 | ポルフィラジン色素、これを含有するインク組成物及び着色体 |
JP5458022B2 (ja) * | 2008-12-25 | 2014-04-02 | 日本化薬株式会社 | ポルフィラジン色素、これを含有するインク組成物及び着色体 |
US8535431B2 (en) | 2008-12-25 | 2013-09-17 | Nippon Kayaku Kabushiki Kaisha | Porphyrazine coloring matter, ink composition containing the same and colored product |
US8535432B2 (en) | 2009-04-15 | 2013-09-17 | Nippon Kayaku Kabushiki Kaisha | Porphyrazine coloring matter, ink composition containing the same and colored product |
JP2011190429A (ja) * | 2010-02-19 | 2011-09-29 | Nippon Kayaku Co Ltd | ポルフィラジン色素、これを含有するインク組成物及び着色剤 |
Also Published As
Publication number | Publication date |
---|---|
JPWO2009084195A1 (ja) | 2011-05-12 |
US7981204B2 (en) | 2011-07-19 |
US20100279082A1 (en) | 2010-11-04 |
JP5281019B2 (ja) | 2013-09-04 |
TWI434893B (zh) | 2014-04-21 |
TW200938593A (en) | 2009-09-16 |
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