WO2007116933A1 - ポルフィラジン色素、インク、インクセット及び着色体 - Google Patents
ポルフィラジン色素、インク、インクセット及び着色体 Download PDFInfo
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- WO2007116933A1 WO2007116933A1 PCT/JP2007/057651 JP2007057651W WO2007116933A1 WO 2007116933 A1 WO2007116933 A1 WO 2007116933A1 JP 2007057651 W JP2007057651 W JP 2007057651W WO 2007116933 A1 WO2007116933 A1 WO 2007116933A1
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/06—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide
- C09B47/067—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile
- C09B47/0675—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile having oxygen or sulfur linked directly to the skeleton
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/06—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide
- C09B47/067—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile
- C09B47/0678—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile having-COOH or -SO3H radicals or derivatives thereof directly linked to the skeleton
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/08—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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- 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
- C09D11/40—Ink-sets specially adapted for multi-colour inkjet printing
Definitions
- Porphyrazine coloring matter ink, ink set and colored body
- the present invention relates to a novel vorfilazine dye, an ink, an ink set, an ink jet recording method using the ink or the ink set, and a colored body.
- an image recording material a material for forming a color image has been mainly used.
- an ink jet recording material a thermal transfer image recording material, a recording material using an electrophotographic method, Transfer-type silver halide photosensitive materials, printing inks, recording pens, etc. are actively used.
- Color filters are used in electronic parts such as LCDs (liquid crystal displays) and PDPs (plasma display panels) in displays and CCDs (imaging devices) in photographic equipment.
- color image recording materials and power filters use so-called additive and subtractive primary colorants (dyes and pigments) to reproduce or record full-color images! ⁇
- additive and subtractive primary colorants dyes and pigments
- the reality is that there is no dye that has an absorption characteristic that can realize a color reproduction range and can withstand various use conditions, and improvement is strongly desired.
- Inkjet recording methods include the continuous method that allows droplets to fly continuously, and the on-demand method that causes droplets to fly in response to image information signals.
- Examples of inks suitable for inkjet recording include water-based inks, oil-based inks, and solid (melting type) inks.
- the requirements for dyes used in inks suitable for such ink jet recording include good solubility or dispersibility in solvents and high density recording Good hue for both single and mixed colors, strong against light, heat, and active gases in the environment (NOx, ozone and other acidic gases such as SOx), Excellent durability against water and chemicals, good fixability to recording materials, difficult to bleed, excellent storability as an ink, no toxicity, and low cost What can be done.
- it has a good cyan hue, is excellent in light resistance (durability to light), ozone resistance (durability to ozone gas) and moisture resistance (durability under high humidity), and is also called bronzing phenomenon (bronzing phenomenon) ), A cyan dye is strongly desired.
- the bronze phenomenon refers to a phenomenon in which pigments aggregate on the surface of glossy paper due to association or aggregation of pigments or poor absorption of ink in the media, resulting in a metallic luster and glare. When this phenomenon occurs, the gloss, print quality, and print density are all poor.
- Typical examples of water-soluble cyan dye skeletons used in inks suitable for inkjet recording include phthalocyanine-based triphenylmethane-based skeletons.
- the most widely reported and utilized phthalocyanine dyes are phthalocyanine derivatives classified as A to H below.
- Known phthalocyanine dyes such as I. Acid Blue 249 or C. I. Reactive Blue 71
- G phthalocyanine dye described in Patent Documents 8, 9, 12, etc.
- Phthalocyanine dyes such as CI Direct Blue 86 or CI Direct Blue 1 99, which are currently widely used, are characterized by superior light resistance compared to commonly known magenta dyes and yellow one dyes. . Phthalocyanine-based dyes have a greenish hue under acidic conditions, which is not preferable for cyan ink. Therefore, when these dyes are used as cyan ink, it is preferable to use them under conditions where the neutral force is also alkaline. However, even if the ink is neutral or alkaline, the hue of the printed matter may change greatly if the recording material used is acid paper.
- the tri-methane group has very good hue, light resistance, ozone resistance and moisture resistance!
- Patent Document 1 Japanese Patent Application Laid-Open No. 62-190273
- Patent Document 2 Japanese Patent Laid-Open No. 7-138511
- Patent Document 4 JP-A-5-171085
- Patent Document 5 Japanese Patent Laid-Open No. 10--140063
- Patent Document 6 Special Table 11--515048
- Patent Document 7 JP 59--22967
- Patent Document 8 JP 2000-303009
- Patent Document 9 JP 2002-249677
- Patent Document 10 Japanese Patent Laid-Open No. 2003-34758
- Patent Document 11 Japanese Patent Laid-Open No. 2002-80762
- Patent Document 12 WO2004087815
- Patent Document 13 WO2002034844
- Patent Document 14 Japanese Patent Application Laid-Open No. 2004-75986
- the present invention provides a novel borphyrazine dye that solves the above problems, has a good hue as a cyan ink, is excellent in light resistance, ozone resistance and moisture resistance, and does not cause bronzing. It is another object of the present invention to provide an ink suitable for ink jet using the coloring matter and an ink jet recording method.
- the present inventors have studied in detail borfilazine dyes having a good hue, high light resistance and ozone resistance, and causing no bronze phenomenon.
- the present invention has been completed by finding that the above-mentioned problems can be solved by using it as a coloring matter for the use. That is, the present invention (1)
- A, B, C and D each independently represent an aromatic 6-membered ring, of which at least one is a benzene ring and at least one of the remaining is a nitrogen-containing heteroaromatic.
- E represents alkylene
- X and Y each independently represent a substituted or unsubstituted arylino group, or a substituted or unsubstituted naphthylamino group, which is a sulfo group.
- the naphthyl amino group which may have 0 to 4 substituents of one kind or two or more kinds selected is a sulfo group, a carboxyl group, a urea group.
- the amount of the organic amine represented by the formula (4) is 0.5 to 4 molar equivalents relative to 1 molar equivalent of the compound of the formula (3), and the pH in the reaction system is adjusted in the presence of ammonia.
- the number of pyridine rings or pyrazine rings corresponding to A, B, C, and D is 1 to 3
- E represents C2 to C4 alkylene
- X and Y are each independently an unsubstituted alkyl A lino group, a sulfo-substituted lino group, a carboxyl-substituted lino group, a phosphono-substituted lino group, an unsubstituted naphthyl amino group, a sulfo-substituted naphthylamino group or a carboxy-substituted naphthylamino group,
- the substituted naphthylamino group is a group force consisting of a sulfo group, a carboxyl group, a phosphono group, a hydroxyl group, an alkoxy group, a ureido group, an acetylylamino
- E represents ethylene or propylene
- X and Y are each independently a sulfo-substituted linrino group, a carboxyl-substituted arlino group or a sulfo-substituted naphthylamino group
- b is 0 force 2.9.
- A is a pyridine ring condensed at the 2-position and 3-position or 3-position and 4-position or a pyrazine ring condensed at the 2-position and 3-position
- B is 2-position and 3-position or 3-position and 4-position
- a pyridine ring or 2-position and 3-position C condensed at the 2-position, 3-position, 3-position and 4-position
- D is a benzene ring
- E is a C2-C4 alkylene
- X and Y are each independently a sulfo group, a carboxy group, a methoxy group
- Z forces Z each independently represent a nitrogen atom or a carbon atom.
- the amount of the organic amine represented by the formula (4) is 0.5 to 4 molar equivalents relative to 1 molar equivalent of the compound of the formula (5), and the pH in the reaction system is adjusted in the presence of ammonia.
- A is a pyridine ring condensed at the 2-position and 3-position
- B is a pyridine ring or benzene ring condensed at the 2-position and 3-position
- C is condensed at the 2-position and 3-position
- D is a benzene ring
- E is a C2-C4 alkylene
- X and Y are each independently a group force consisting of a sulfo group and a carboxy group.
- the amount of the organic amine represented by the formula (4) is 0.5 to 4 molar equivalents relative to 1 molar equivalent of the compound of the formula (3), and the reaction is carried out in the pH range of 7 to 10.
- the amount of the organic amine represented by the formula (4) is 0.5 to 4 molar equivalents relative to 1 molar equivalent of the compound of the formula (5), and the reaction is carried out in the pH range of 7 to 10.
- Porphyrazine coloring power One or two of A, B, C and D is a nitrogen-containing heterocyclic ring or a pyridine ring, and the remainder is a benzene ring, the borphyrazine coloring matter according to (1) to (11), or A , B, C, and D are nitrogen-containing heterocycles or pyridine rings, and the rest are benzene rings.
- Borfilazine dyes according to (1) to (11) and two of A, B, C, and D are nitrogen-containing heterocycles Or a borfirazine dye or a salt thereof according to (1) to (11), which is a mixture of a pyrrolidine dye described in (1) to (11) and a powerful dye mixture described in (1) to (11), wherein the pyridine ring and the remaining two are benzene rings.
- the ink using the compound of the present invention has an excellent hue as a cyan ink and is excellent in light resistance, ozone resistance and moisture resistance. In addition, it has good storage stability without crystal precipitation, changes in physical properties, and color changes after long-term storage. In addition, when used with other magenta inks and yellow inks, it has a wide visible color tone, especially with magenta inks. When used, the hue of blue can be broadened. Accordingly, the cyan ink using the porphyrazine coloring matter of the present invention is extremely useful as an ink for ink jet recording.
- An ink suitable for ink jet recording according to the present invention is characterized by containing the borphyrazine dye of the formula (1).
- tetrabenzoborphyrazine usually called phthalocyanine
- phthalocyanine in which one to three benzo rings are replaced with nitrogen-containing heteroaromatic rings
- Ink using borphyrazine dyes with a sulfamoyl group and a substituted sulfamoyl group is extremely resistant to ozone gas and hardly causes bronzing, and has a wider blue hue when used with magenta ink. This is what we found out.
- alkyl the preferred number of carbons varies depending on the use situation. Generally, it is about 1-20, preferably about 1-10, and in the case of aryl, it varies depending on the use situation.
- it is an aromatic ring group having about 6 to 14 carbon atoms, preferably 6 to: an aromatic ring group having about LO, and specific examples include a full group or a naphthyl group.
- examples of the halogen atom include a chloro atom, a bromine atom, and an iodine atom, and a chloro atom is usually preferable.
- examples of the heterocycle include about 3 to 10 rings containing heteroatoms such as oxygen atoms, nitrogen atoms and / or sulfur atoms.
- the nitrogen-containing heteroaromatic ring in the 6-membered aromatic rings A to D includes, for example, 1 to 2 nitrogen atoms such as a pyridine ring, a pyrazine ring, a pyrimidine ring or a pyridazine ring. Including 6-membered aromatic rings. Of these, the pyridine ring is most preferred.
- 1 to 3 of A to D are nitrogen-containing heteroaromatic rings, and the rest are benzene rings.
- the nitrogen-containing heteroaromatic rings As the number of nitrogen-containing heteroaromatic rings increases, the ability to improve ozone resistance tends to occur.Bronzing properties tend to occur, and the number of nitrogen-containing heteroaromatic rings is appropriately determined in consideration of ozone resistance and bronzing properties. Adjust and select a well-balanced ratio.
- the nitrogen-containing heteroaromatic ring has an average value of 1 to 2.5, more preferably 1 to 2
- the rest are benzene rings A compound.
- the number of nitrogen-containing heteroaromatic rings is one compound, or the one compound and two or Z and three compounds.
- a dye mixture consisting of a mixture with is a preferred embodiment.
- One of the more preferred embodiments is a mixture of a compound having one nitrogen-containing heteroaromatic ring and two compounds among four of A to D.
- the mixture power of the compound having one nitrogen-containing heteroaromatic ring and two or Z and three compounds, and the ratio of both of the dye mixture, the molar ratio, the number of nitrogen-containing heteroaromatic rings is 1
- the amount of 2 or Z and 3 compounds (more preferably 2 compounds) is 0 to 3 mol, more preferably 0 to 2 mol, still more preferably 0 to 1 mol, per mol of one compound.
- b is 0 force 2.9
- c is 0.1 to 3
- the sum of b and c is 1 to 3.
- the resistance to ozone resistance tends to improve.Bronzing tends to occur more easily.
- the number of b and c is adjusted as appropriate, Select a good ratio.
- Preferred c is from 0.1 to 2.5, and the rest is b.
- Examples of the alkylene in E include alkylene having 2 to 12 carbons, and more preferably alkylene having 2 to 6 carbons. Specific examples include ethylene, propylene, butylene, pentylene, hexylene, cyclopropylene diyl, 1,2- or 1,3-cyclopentylene distillate, 1,2-, 1,3-, or 1,4- Examples include cyclohexylene. . Preference is given to ethylene, propylene or butylene. More preferred is ethylene or propylene, and still more preferred is ethylene.
- X and Y each independently represent an unsubstituted or substituted carino group or an unsubstituted or substituted naphthylamino group.
- substituent of the substituted arino group include a sulfo group, a carboxyl group, a phosphono group, a strong rubamoyl group, a sulfamoyl group, a ureido group, an alkyl group, an alkoxy group, an aryloxy group, a hydroxyl group, a dialkylamino group, and an alkylamino group.
- a arylamino group, a acetylamino group, a cyano group, a nitro group, a halogen atom, and a heterocyclic group, and 1 to 4 kinds of substituents may be used.
- substituents examples thereof include a sulfo group, a carboxyl group, and a hydroxyl group. More preferred substituents are a sulfo group and / or a carboxyl group.
- Examples of the substituent of the substituted naphthylamino group include a sulfo group, a carboxyl group, a ureido group, an alkyl group, an alkoxyl group, a hydroxyl group, a dialkylamino group, an alkylamino group, an aryl group, a acetylamino group, a cyano group, a nitro group, a halogen atom, Heterocyclic groups are exemplified, and one to two or more kinds of substituents may be included among these.
- Preferred examples of the substituent include a sulfo group and a hydroxyl group.
- the salt of the compound of formula (1) is preferably an inorganic or organic cation salt.
- examples of salts include alkali metal salts, alkaline earth metal salts, and ammonium salts. This Among these salts, preferred are alkali metal salts, specifically lithium, sodium or potassium salts.
- Examples of the alkaline earth metal of the alkaline earth metal salt include calcium and magnesium.
- Examples of organic amines include lower alkylamines having 1 to 3 carbon atoms such as methylamine and ethylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, and the like.
- Preferred salts include alkali metal salts such as sodium salt, potassium salt and lithium salt, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine and the like. Examples include di- or tri- (lower C1 carbon lower alcohol) ammine salt and ammonia salt.
- A, B, C, D, E, X and ⁇ in the porphyrazine dye represented by the above formula (1) of the present invention are shown in Table 1, and borphyrazine used in the present invention
- the dye is not limited to the following examples.
- the nitrogen-containing heteroaromatic ring corresponding to A, B, C, and D is a pyridine ring
- These isomers are difficult to isolate, and it is difficult to identify isomers by analysis. For this reason, the mixture is usually used as it is, but even if it is a mixture of isomers, no particular problem is caused in the present invention. Therefore, these isomers are described without distinction.
- a conventionally known method can be applied to synthesize the copper borfylazine dye represented by the above formula (6).
- it can be obtained by reacting an aromatic 6-membered nitrogen-containing heteroaromatic dicarboxylic acid derivative with a phthalic acid derivative in the presence of a catalyst and a copper compound.
- the nitrogen-containing heteroaromatic rings and the number of benzene rings in A, B, C, and D by changing the molar ratio of the reaction between the nitrogen-containing heteroaromatic dicarboxylic acid derivative and the phthalic acid derivative.
- the nitrogen-containing heteroaromatics depend on the content ratio.
- the cyclic dicarboxylic acid derivative and the phthalic acid derivative in the ratio of 0.25 mol to 0.75 mol, respectively, so that the total of both is 1 mol, the target compound Can be obtained.
- the nitrogen heteroaromatic dicarboxylic acid derivative may be used at a ratio of 0.25 mol and the phthalic acid derivative at 0.75 mol.
- Nitrogen-containing heteroaromatic dicarboxylic acid derivatives include a carboxyl group or a reactive group derived therefrom (acid amide group, imide group, acid anhydride group, carbo-tolyl group, etc.) at two adjacent positions. And a 6-membered nitrogen-containing heteroaromatic dicarboxylic acid derivative.
- dicarboxylic acid compounds such as quinolinic acid, 3,4 pyridinedicarboxylic acid, 2,3 pyrazinedicarboxylic acid, quinolinic anhydride, 3,4-pyridinedicarboxylic acid anhydride, 2,3 pyrazinedicarboxylic acid anhydride, etc.
- Acid anhydride compounds dicarboxyamide compounds such as pyridine 2,3-dicarboxamide, dicarboxylic acid monoamide compounds such as pyrazine-2,3-dicarboxylic acid monoamide, acid imido compounds such as quinolinic acid imide, Dicarbohydrates such as pyridine-2,3-dicarbonitryl and pyrazine-2,3-dicarbonitryl Nitorirui compound.
- dicarboxyamide compounds such as pyridine 2,3-dicarboxamide
- dicarboxylic acid monoamide compounds such as pyrazine-2,3-dicarboxylic acid monoamide
- acid imido compounds such as quinolinic acid imide
- Dicarbohydrates such as pyridine-2,3-dicarbonitryl and pyrazine-2,3-dicarbonitryl Nitorirui compound.
- phthalic acid derivatives phthalic acid and phthalic anhydride
- Phthalamide phthalamic acid, phthalimide, phthalonitrile, 1,3 diminoisoindrin, 2-cyanobenzamide, and the like.
- Methods for synthesizing copper borphyrazine dyes are generally referred to as the -tolyl method and the Weiler method, and the reaction conditions are different.
- the nitrile method is a method for synthesizing borphyrazine dyes from dicarbo-tolyl compounds such as pyridine 2,3 dicarbo-tolyl, pyrazine-2,3-dicarbo-tolyl, and lid mouth-tolyl.
- the Weiler method uses dicarboxylic acid compounds such as phthalic acid, quinolinic acid, 3,4 pyridinedicarboxylic acid, 2,3 pyrazinedicarboxylic acid, phthalic anhydride, quinolinic anhydride, 3,4 pyridinedicarboxylic anhydride, 2 , 3-acid anhydride compounds such as pyrazine dicarboxylic acid anhydride, dicarboxyamide compounds such as phthalamide and pyridine 2,3-dicarboxamide, phthalamic acid, dicarboxylic acid such as pyrazine mono 2,3-dicarboxylic acid monoamide, etc.
- dicarboxylic acid compounds such as phthalic acid, quinolinic acid, 3,4 pyridinedicarboxylic acid, 2,3 pyrazinedicarboxylic acid, phthalic anhydride, quinolinic anhydride, 3,4 pyridinedicarboxylic anhydride, 2 , 3-acid anhydride compounds such as
- Acid imide compounds such as acid monoamide compounds, phthalimide and quinolinic acid imide are used as raw materials.
- addition of urea is essential, and the amount of urea used is 5 to 100 times the molar amount of the total of 1 mole of nitrogen-containing heteroaromatic dicarboxylic acid derivative and phthalic acid derivative.
- 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 as the solvent.
- n-amyl alcohol, n-hexanol, cyclohexanol, 2-methanol 1-pentanol, 1-heptanol, 1-octanol, 2-ethylhexanol, N, N-dimethylaminoethanol examples thereof include benzenoreanolol, ethylene glycol, propylene glycol, chlorobenzene, 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 as the solvent.
- examples thereof include triclonal benzene, black naphthalene, nitrobenzene, quinoline, sulfolane, and urea.
- the amount of solvent used is 1 to 100 times the total amount of the nitrogen-containing heteroaromatic dicarboxylic acid derivative and the phthalic acid derivative.
- Examples of the copper compound include copper metal, or copper compounds such as copper halides, carboxylates, sulfates, nitrates, acetylacetonates, and complexes.
- Examples of the copper compound include copper chloride, copper bromide, copper acetate, copper acetyl cetate and the like. The amount of copper compound used is 0.15 to 0.35 times the mole of a total of 1 mole of nitrogen-containing heteroaromatic dicarboxylic acid derivative and 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.
- the main component is copper dibenzobis (2,3 pyrido) borfylazine, which includes five isomers having different positions of the pyridine ring and the nitrogen atom of the pyridine ring. ⁇ Expressions (7—A) to (7—E) ⁇ are generated.
- one of A to D in the above formula (6) is a copper tribenzo (2,3 pyrido) borfilazine represented by a pyridine ring and the remaining three are benzene rings ⁇ Formula (8) ⁇ And three of A to D in formula (6) are pyridine Copper benzotris (2,3 pyrido) porphyrazine, one of which is a benzene ring, is formed as a by-product of the ring, and these compounds also have positional isomers of the pyridine ring nitrogen atom (formula (9 A) ⁇ (9—D) ⁇ is present, resulting in a complex mixture.
- the nitrogen-containing heteroaromatic ring is 1 or 3 compounds, or a mixture of one compound and 2 or / and 3 compounds, etc.
- the nitrogen-containing heteroaromatic ring dicarboxylic acid The proportions of the derivative and phthalic acid derivative are in the range of approximately 0.25 mol to 0.75 mol, and the total amount of both is 1 mol. It can be obtained in the same way by changing according to the ratio.
- the copper chlorosulfonylporphyrazine compound represented by the formula (3) is obtained by chlorosulfonating a copper porphyrazine dye represented by the formula (6) in chlorosulfonic acid, or It is obtained by converting the sulfo group to a chlorosulfone group with a chlorinating agent after sulfonation in the sulfuric acid or fuming sulfuric acid.
- the chlorosulfone group or sulfo group thus obtained is introduced onto the benzene ring in A to D of formula (6), and is not introduced into the heteroaromatic ring group of A to D.
- a sulfo ring represented by the following formula (11) can be obtained by condensing and ring-closing with sulfophthalic acid having a sulfo group and quinolinic acid in advance.
- the target compound of formula (3) can also be obtained by synthesizing a copper borphyrazine dye having a group and then converting the sulfo group to a chlorosulfone group.
- the number (n) of SO C1 groups in the obtained compound of formula (3) is 1 to 3 on average as described above, and preferably 2 to 3 on average.
- the conditions for the chlorosulfonation reaction of the copper porphyrazine dye are usually chlorosulfonic acid as a solvent, and the amount used is 3 to 20 times by weight, preferably 5 to 10 times the weight of the porphyrazine dye.
- 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 and is usually 1 to 10 hours. In this case, since the substituent of the obtained copper borohydrazine compound is a mixture of a chlorosulfone group and a sulfo group, in the present invention, the reaction solution with chlorosulfonic acid is used so that all the sulfo groups are chlorosulfonated.
- a chlorinating agent such as chloro chloride other than chlorosulfonic acid.
- the amount of the chlorinating agent other than chlorosulfonic acid to be added is about 0.5 to 10 equivalents, preferably about 0.5 to 5 equivalents, relative to the sulfo group in the sulfo-substituted copper borfylazine dye.
- the chronorelating agent includes, but is not limited to, chlorosulfonic acid, thiol chloride, sulfuryl chloride, phosphorus trichloride, phosphorus pentachloride and phosphorus oxychloride.
- Solvents used in the Chloroyl reaction include sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, benzene, toluene, nitrobenzene, black benzene, N, N-dimethylformamide, N, N-dimethylacetamide, etc. Is not to be done.
- the chlorinating agent includes, but is not limited to, chlorosulfonic acid, thiol chloride, sulfuryl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride and the like.
- the copper chlorosulfol porphyrazine compound obtained above (hereinafter also simply referred to as a chlorosulfonyl compound) and an organic amine represented by the following formula (4) are added in the presence of ammonia. (Or in the presence of an aminating agent) in a water solvent, usually pH 7-10, preferably pH 8-10, usually 0-100 ° C, preferably 5-70 ° C, usually 1-20 hours.
- an aminating agent in a water solvent, usually pH 7-10, preferably pH 8-10, usually 0-100 ° C, preferably 5-70 ° C, usually 1-20 hours.
- Ammonia used in the reaction or Examples of ammonia generation sources include ammonia salts such as ammonium chloride and ammonium sulfate, urea, aqueous ammonia, and ammonia gas. It is not limited to.
- the reaction of copper chlorosulfol porphyrazine compound, organic amine and aminating agent is usually carried out in an aqueous solvent.
- For the pH adjustment during the condensation for example, 28% ammonia water, which is available as a commercial product, can be used directly or diluted with water as necessary.
- the compound in which p is 3 in the above formula (11) is led to a chlorosulfol derivative, and then the chlorosulfo derivative is introduced.
- the pH in the reaction system is adjusted to alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and alkali metals such as sodium carbonate and potassium carbonate. It is also possible to obtain a compound of the above formula (1) in which the target b is 2 and c is 1 by adjusting and reacting with a carbonate of
- the pH in the reaction system is usually 7 to 10, preferably 7.5 to 10, and more preferably 8 to 9.5.
- the chlorosulfonyl compound is hydrolyzed to increase the ratio of the by-product sulfonic acid derivative. If the amount is too large, hydrolysis of the chlorosulfuric acid occurs, and when excess ammonia is present in the reaction system, the ammonia preferentially reacts with the chlorosulfuric acid, resulting in an organic amine of the following formula (4). There is a tendency for the reaction rate between chlorosulfol and chlorosulfol to be significantly reduced.
- the ratio of adding ammonia, the organic amine of the following formula (4) and the chlorosulfur compound, and the pH in the reaction system should be set appropriately in consideration of these points.
- the amount of the organic amine represented by the above formula (4) is usually 0.5 to 4 molar equivalents of the theoretical value with respect to 1 mol of the copper chlorosulfol porphyrazine compound, preferably 0.5 molar equivalent to 3.5 molar equivalent, more preferably 1 molar equivalent to 3 molar equivalent. However, it varies depending on the reactivity and reaction conditions of the organic amine, and is not limited thereto.
- an aline or naphthylamine corresponding to X is usually from 0.95 to: 1 mol of L and 2,4,6 trichlorine S triazine (cyanuryl chloride) in water, usually pH 3-7, The reaction is usually carried out at 5 to 40 ° C for 2 to 12 hours to obtain a primary condensate.
- the secondary reaction is carried out by reacting the phosphines or naphthylamines corresponding to Y usually 0.95-1.1 mol, usually pH 4-10, usually 5-80 ° C, usually 0.5-12 hours. A condensate is obtained.
- alkylenediamine corresponding to E is reacted usually at pH 9-12, usually 5-90 ° C, usually 0.5-8 hours to obtain the organic amine of the above formula (4). It is done.
- the pH adjustment during the condensation usually includes alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and alkali metal carbonates such as sodium carbonate and potassium carbonate.
- the order of condensation is appropriately determined according to the reactivity of various compounds, and is not limited to the above.
- the copper borphyrazine dye represented by the formulas (1) and (2) is represented by the copper chlorosulfol porphyrazine compound represented by the formula (3) and the formula (4). Since the organic amine is synthesized by reacting in the presence of ammonia (or in the presence of an aminating agent), it is hydrolyzed with water in which the chlorosulfol compound of formula (3) is partially mixed in the reaction system. It is theoretically considered that the compound converted to sulfonic acid by decomposition is by-produced and mixed into the target dyes of the formulas (1) and (2).
- the copper borphyrazine dyes represented by the above formulas (1) and (2) are partly dimerized (for example, Pz-L) via a divalent linking group (L). Impurities that form Pz) or trimers are by-produced and may be mixed into the reaction product.
- Examples of the divalent linking group represented by L include S02— and —S02—NH—S02. In the case of a trimer, a byproduct formed by combining these two Ls is formed. It may be done.
- the formula of the present invention derived from copper tetrax (2,3-pyrido) porphyrazine and copper phthalocyanine (copper tetrabenzoporphyrazine) described as being produced in a small amount during the synthesis of copper borphyrazine described above.
- Copper tetrakis (2,3-pyrido) borfilazine and copper phthalocyanine (copper tetrabenzoborfilazine) having an unsubstituted sulfonamide group and a substituted sulfonamide group in 1) are also sometimes by-produced.
- These by-products including copper tetrakis (2,3-pyrido) borfylazine, which are by-produced in a small amount during the synthesis of copper borphyrazine, are within 35% of the total synthetic pigment, usually within 30%. Preferably it is about 15% or less. Since these by-products are all pigments, they are also referred to as by-product pigments in this specification.
- these by-product dyes for example, copper phthalocyanine (copper tetrabenzoporphyrazine) having an unsubstituted sulfonamide group and a substituted sulfonamide group in the formula (1) of the present invention is at most 0 to 35%. Within the range, usually 0 to 30%. Further, the balance of the force that may contain about 0 to 15% of other by-product dyes is a copper borphyrazine dye represented by the formula (1) in the invention.
- the dye of the present invention is usually 65% to 100%, more preferably 85% to 100%, optionally 85 to 99%, and by-product dye 0 to 35% of the formula (1). More preferably, it is obtained as a dye mixture containing 0 to 15%, optionally 1 to 15%.
- the thus obtained copper borphyrazine dye of the present invention can be separated by filtration or the like after aciding out or salting out.
- salting out is preferably performed in the range of acidic to alkaline, preferably pH 1 to L 1.
- the temperature at the time of salting out is not particularly limited, but it is preferable that salting out is usually carried out by adding salt after heating to 40 to 80 ° C, preferably 50 to 70 ° C.
- the copper porphyrazine coloring matter represented by the above formulas (1) and (2) 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.
- a salt when salting out or a desired salt cannot be obtained by salting out, for example, a normal salt exchange method in which a desired organic or inorganic base is added to a free acid is used. If you do.
- Preferred porphyrazine dyes represented by the formula (1) or (2) of the present invention are 1 to 3, preferably 1 to 2 of A to D are pyridine rings or pyrazine rings (more preferably pyridine rings). ), The sum of b and c is 2 to 3, c is 0.1 to 2.5, and the rest is b (more preferably b and the sum of c is 3, c is 1 to 2.5, b is 0.5 to 2), X is a sulfoa-lino group or a sulfonaphthyl group (more preferably, a sulfoa-lino group), These may be further substituted with 1 to 2 groups selected from the group force of sulfo group and carboxyl group.
- Y is 1 to 2 groups selected from the group consisting of sulfo group and carboxyl group. This is a case of a substituted linrino group (more preferably, a sulfor-lino group). Of these, V is preferred, V and other combinations, particularly preferred, 2 or 3 combinations of things are more preferred.
- the borphyrazine dye represented by the formula (1) of the present invention can be used in combination with a conventional phthalocyanine dye.
- the borphyrazine dye of the present invention is 50-100%, preferably 70-: LOO%, more preferably 90-: LOO%, a conventional phthalocyanine dye 0-50%, preferably 0-30%, more preferably. Is about 0-10%.
- the conventional phthalocyanine dye any of the phthalocyanine dyes described in the section of the prior art can be used.
- the borphyrazine dye of the above formula (1) or a salt thereof produced by the above method exhibits a clear cyan color. Therefore, ink containing these can also be used mainly as cyan ink.
- the ink is a low-density cyan ink (such as light cyan ink or light cyan ink) that is used to smoothly reproduce the tonal portion of an image that is applied with force as a high-density cyan ink, or to reduce graininess in light-colored areas. This is called photocyan ink).
- the ink of the present invention is prepared using water as a medium.
- the borfylazine dye used therein (hereinafter, in the present invention, in the case of simply referred to as a porfirazine dye, unless otherwise specified, a free borfirazine dye, a salt thereof, or a free one) are preferably used in the meaning of including any case of a mixture of a salt and a salt), and those having a small content of anions such as C ⁇ ⁇ and SO 2 are preferred.
- the standard of its content is
- desalting may be performed by a method such as stirring the wet cake in a mixed solvent of alcohol and water.
- the alcohol used 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.
- Borufuirajin dyes of the invention which are desalted alcohols and a mixed solvent of water, by a conventional method, filtered and separated, and then by drying, Borufuiraji less present invention with C1- and SO 2_ content in the dry state
- Borufuiraji emissions dyes used therein in addition to the content of the cr and so 2_, such as zinc and / or iron heavy metal (I
- Metals such as calcium (ions); Silica and the like having a low content are preferable (except for copper contained in the porphyrazine skeleton by ionic bonds or coordinate bonds as a central metal atom).
- a preferable standard for the content is, for example, about 500 ppm or less for each of the above-exemplified heavy metals (ions), metals such as calcium (ions), silica, and the like in the purified dried product of borphyrazine pigment.
- the contents of heavy metals (ions) and metals (ions) are measured by ion chromatography, atomic absorption method or ICP (Inductively Coupled Plasma) emission analysis.
- the ink of the present invention usually contains 0.1 to 8% by mass, preferably 0.3 to 6% by mass, of the vorfilazine dye of the formula (1). If necessary, the ink of the present invention may further contain a water-soluble organic solvent within a range that does not impair the effects of the present invention. Usually, it is preferable to include a water-soluble organic solvent. Water-soluble organic solvents are used as dye solubilizers, drying inhibitors (wetting agents), viscosity modifiers, penetration enhancers, surface tension modifiers and / or antifoaming agents.
- other ink preparation agents include, for example, antiseptic / antifungal agents, pH adjusting agents, chelating reagents, antifungal agents, ultraviolet absorbers, viscosity adjusting agents, dye dissolving agents, anti-fading agents, An emulsion stabilizer, a surface tension adjuster, an antifoaming agent, a dispersant, a dispersion stabilizer, and the like may be added.
- the content of the water-soluble organic solvent (based on the whole ink) is 0 to 60% by mass, preferably 10 to 50% by mass.
- the content of the ink preparation agent (based on the whole ink) is 0-20 mass %, Preferably 0 to 15% by mass.
- the balance is water.
- water-soluble organic solvent examples include C1-C4 alkyl alcohols 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; heterocyclic ketones such as 2 pyrrolidone, N-methyl-2 pyrrolidone, 1,3 dimethylimidazolidin 2 on or 1,3 dimethylhexahydropyrimido 2 on ; Ketone or ketoalcohol such as acetone, methylethylketone, 2-methyl-2 hydroxypentane-4-one; cyclic ether such as tetrahydrofuran, dioxane; ethylene glycol, 1, 2 or 1, 3 propylene glycol, 1, 2 Or 1,4-butylene glycol, 1,6-hexylene glycol;
- hexane-polyols such as triols such as 1, 2, 6 triol; ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, diethylene glycol monomethyl ether or diethylene glycol monoethyl ether or jetylene glycol monobutyl ether or triethylene polyhydric alcohols (C1 -C4)
- Monoa Ruki ethers such as glycol monomethyl ether or triethylene glycol monomethyl E chill ether; I one Chirorataton or dimethyl sulfoxide and the like.
- water-soluble organic solvent is isopropanol, glycerin, modified di- or triethylene glycol, dipropylene glycol, 2-pyrrolidone, or ⁇ ⁇ ⁇ -methyl-2 pyrrolidone, more preferably isopropanol, Glycerin, diethylene glycol or 2-pyrrolidone.
- water-soluble organic solvents are used alone or in combination.
- Examples of the antiseptic / antifungal agent include organic sulfur, organic nitrogen sulfur, organic halogen, halogenylsulfone, odopropargyl, haloalkylthio, benzothiazol, nitrile, pyridine, 8-oxyquinoline, isothiazoline, dithiol, pyridine oxide, nitropropane, organotin, phenol, 4th ammonia
- Examples thereof include salts, triazines, thiadiazines, anilides, adamantanes, dithiocarbamates, brominated indanones, benzyl bromacetates and inorganic salts.
- Examples of the organic halogen compound include sodium pentachlorophenol, examples of the pyridine oxide compound include sodium 2-pyridinethiol 1 oxide, and examples of the isothiazoline compound include 1,2-benzisothiazoline 1 3. —One, 2— n—octyl 4—isothiazoline 1—3-one, 5 chloro 2—methylolene 4 isothiazoline—3 on, 5 chloro 2—methylolene 4 isothiazoline 1—3 on magnesium chloride, 5 chloro 2—methyl 4 isothiazoline 3 On-calcium chloride, 2-methyl 4-isothiazoline 3-on-calcium chloride, and the like.
- Examples of other antiseptic / antifungal agents include sodium acetate, sodium sorbate or sodium benzoate.
- Other specific examples of the antiseptic / antifungal agent include, for example, trade names Proxel R TM GXL (S) and Proxel RTM XL-2 (S) manufactured by Avecia.
- the pH adjuster adjusts the pH of the ink from 6.0 to L: 1. to improve the storage stability of the ink.
- alkanolamines such as diethanolamine or triethanolamine
- alkali metal hydroxides such as lithium hydroxide, sodium hydroxide or potassium hydroxide
- ammonium hydroxide or carbonic acid
- alkali metal carbonates such as lithium, sodium carbonate, and potassium carbonate.
- Examples of the chelating reagent include sodium ethylenediamine tetraacetate, sodium nitrate triacetate, sodium hydroxyethyl ethylenediamine triacetate, sodium diethylenetriaminepentaacetate, sodium uracil diacetate, and the like.
- Examples of the antifungal agent include acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropyl ammonium nitrite, pentaerythritol tetranitrate, and dicyclohexyl ammonium nitrite.
- an ultraviolet ray typified by a benzophenone compound, a benzotriazole compound, a cinnamic acid compound, a triazine compound, a stilbene compound, or a benzoxazole compound is absorbed.
- Fluorescent compounds so-called fluorescence It is possible to use a brightener.
- examples of the viscosity modifier include water-soluble polymer compounds in addition to water-soluble organic solvents, and examples thereof include polybutyl alcohol, cellulose derivatives, polyamines, and polyimines.
- Examples of the dye solubilizer include urea, epsilon prolactam, ethylene carbonate, and the like.
- the anti-fading agent is used for the purpose of improving image storage stability.
- various organic and metal complex anti-fading agents can be used.
- organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, aryls, amines, indanes, chromans, alkoxylins or heterocycles
- metal complex include a nickel complex and a zinc complex.
- Examples of the surface tension adjusting agent include a surfactant, such as an anionic surfactant, an amphoteric surfactant, a cationic surfactant, and a non-ionic surfactant.
- Ryoon surfactants include alkyl sulfocarboxylates, ⁇ -olefin sulfonates, polyoxyethylene alkyl ether acetates, ⁇ -acyl amino acids and their salts, ⁇ -acylmethyl taurate, alkyl sulfates Salt polyoxyalkyl ether sulfate, alkyl sulfate polyoxyethylene alkyl ether phosphate, rosin acid sarcophagus, castor oil sulfate ester salt, lauryl alcohol sulfate ester salt, alkylphenol type phosphate ester, alkyl type phosphate Examples thereof include esters, alkylaryl sulfonates, jetyl sulfonates, jetyl hex
- Cationic surfactants include 2-bulupyridine derivatives or poly-4-vinylpyridine derivatives.
- Amphoteric surfactants include lauryl dimethylaminoacetic acid betaine, 2-anolequinole- ⁇ -canoleboxoxymethinole- ⁇ -hydroxyethylimidazolium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine Or polyoctylpolyaminoethyldaricin, and other imidazoline derivatives.
- the non-ionic surfactant include polyoxyethylene nouryl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene monomer.
- Ether-based compounds such as tilphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether or polyoxyethylene alkyl ether; polyoxyethylene oleic acid; polyoxyethylene oleate, polyoxyethylene distearate , Ester forms such as sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquilate, polyoxyethylene monooleate or polyoxyethylene stearate; 2, 4, 7, 9-tetramethyl-5 decyne-4, Acetylene glycols such as 7-diol, 3, 6-dimethyl-4-octyne-3, 6-diol, 3,5-dimethyl 1, 1-hexyne 3ol (for example, Surfinol RTM manufactured by Nissin Chemical Industry Co., Ltd.) 104, 82, 465, Ol In R TM STG and the like); and the like can be mentioned, et al are.
- 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 of the present invention is usually 25 to 70 mNZm, more preferably 25 to 60 mNZm.
- the viscosity of the ink of the present invention is preferably 30 mPa ⁇ s or less. Furthermore, it is more preferable to adjust to 20 mPa's or less.
- the order in which the respective drugs are dissolved is not particularly limited.
- the water used is preferably one having few impurities such as ion-exchanged water or distilled water.
- microfiltration may be performed using a membrane filter to remove impurities.
- the pore size of the filter for performing microfiltration is usually 1 micron to 0.1 micron, preferably 0.8 micron to 0.2 micron.
- the ink of the present invention can be used not only for the formation of a single color image but also for the formation of a full color image.
- a full-color image it can be used as a three-primary color ink set obtained by adding the cyan ink of the present invention to the magenta ink and yellow ink, and further as a four-color ink set obtained by adding the black ink thereto.
- a light magenta ink, a blue ink, a green ink, an orange ink, a dark yellow ink, and / or a gray ink and the like are combined with the cyan ink of the present invention. It can also be used as a set.
- a coupling component there are allylazo dyes having aryl compounds such as phenols, naphthols or aryls, or heterocyclic compounds such as pyrazolone and pyridone.
- arylazo dyes such as phenols, naphthols or aryls
- heterocyclic compounds such as pyrazolone and pyridone.
- benzylidene dyes other than heteroarylazo dyes and azo dyes methine dyes such as monomethineoxonol dyes
- quinone dyes such as naphthoquinone dyes and anthraquinone dyes
- examples of other dye species include quinophthalone dyes, nitro'nitroso dyes, atalidine dyes, and ataridinone dyes.
- arylene dyes having arylene compounds such as phenols, naphthols and / or aryls as coupler components; heteroazo dyes having the above arylene compounds as coupler components; pyrazolones or pyrazolotria as coupler components Azomethine dyes having sols and the like, and methine dyes such as arylidene dyes, styryl dyes, merocyanine dyes, cyanine dyes or oxonol dyes other than azo dyes; Um dyes; quinone dyes such as naphthoquinone, anthraquinone or anthrapyridone; condensed polycyclic dyes such as dioxazine dyes;
- each of the above-mentioned dyes may exhibit yellow, magenta, and cyan colors only after a part of the chromophore is dissociated.
- the counter force thione may be an alkali metal or ammonia. Or an organic cation such as pyridinium or quaternary ammonium salt. Further, it may be a polymer cation having such a cation as a partial structure.
- black coloring matter in the black ink examples include a disazo, trisazo or tetraazo dye, a carbon black dispersion, and the like.
- the ink of the present invention can be used in recording methods such as printing, copying, marking, writing, drawing, and stamping, and is particularly suitable for use in ink jet printing.
- the ink prepared as described above contains energy.
- One is dispensed and ink drops are ejected onto the image receiving material to form an image.
- the image receiving material also referred to as coloring material or recording material in the present invention
- known image receiving materials that is, plain paper, oil-coated paper, ink jet paper, glossy paper, glossy film, electrophotography Examples include common paper, fiber and cloth (cellulose, nylon, wool, etc.), glass, metal, ceramics or leather.
- a polymer fine particle dispersion (also referred to as polymer latex) may be used.
- the timing of applying the polymer latex to the image receiving material may be before, after or at the same time as image formation. Therefore, whether the liquid substance of the polymer latex alone is applied to the image receiving material before or after image formation, or the image receiving material in which the polymer latex is pre-mixed is used, it is further incorporated into the ink. However, the ink may be applied to the image receiving material.
- the colored product of the present invention is obtained by coloring an image receiving material with the above vorfilazine dye of the present invention or an ink containing the same.
- the material to be colored is not particularly limited as long as it is an article that can be colored with the vorfilazine dye of the present invention.
- information transmission sheets such as paper and film, fibers and fabrics (cellulose, nylon, wool, etc.), leather, base materials for color filters, and the like.
- the information transmission sheet is preferably a surface-treated sheet, specifically, a sheet, synthetic paper, or a substrate such as a film 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, or by absorbing inorganic fine particles such as porous silica, alumina sol, and special ceramics that can absorb the dye in the ink. It is provided by coating the surface of the base material together with a hydrophilic polymer such as polybulurpyrrolidone.
- a hydrophilic polymer such as polybulurpyrrolidone.
- Those provided with such an ink-receiving layer are usually called inkjet paper (film), glossy paper (film) and the like. Among them, it is said that it is easily affected by gases with an acid action in the air, such as ozone gas.
- typical off-the-shelf products are Pi-Co Rico R TM (trade name: manufactured by Asahi Glass Co., Ltd.), professional photo paper, super photo paper, and mat photo paper.
- Ippa both trade names: manufactured by Canon Inc.
- photo paper Krispia R TM high gloss>, photo paper high gloss> and photo matte paper all trade names: manufactured by Seiko Epson Corporation
- Advanced Photo Paper glossy
- premium glossy film or photo paper both trade names: Nippon Hewlett Packard Co., Ltd.
- Photolike QP trade name: Coca Co., Ltd.
- photo gloss There are paper (both are trade names: Sony Corporation).
- plain paper can also be used.
- Any coloring method for obtaining the colored product of the present invention may be used.
- One preferable coloring method is a method (recording method) of coloring a material to be colored with the ink using an ink jet printer.
- the colorant is not particularly limited as long as it is an article that can be colored by the recording material and other ink jet printers.
- a container containing the above-mentioned ink is set at a predetermined position of the ink jet printer, and is subjected to the usual method. What is necessary is just to record on a recording material.
- the ink jet printer include a piezo type printer using mechanical vibration and a public jet RTM (registered trademark) type printer using bubbles generated by heating.
- the ink according to the present invention does not precipitate or / and separate during storage.
- the ejector ink head
- the ink according to the present invention causes changes in physical properties even when used for printing for a relatively long time and under a constant recirculation by a continuous ink jet printer, or for intermittent printing by an on-demand ink jet printer. Absent.
- the ink of the present invention has a clear cyan color, and by using the ink, a recorded matter particularly excellent in ozone resistance and light resistance and water resistance can be obtained.
- a recorded matter particularly excellent in ozone resistance and light resistance and water resistance can be obtained.
- it can be used with other yellow, magenta, and other green, red, orange, blue, etc. inks that are excellent in ozone resistance, light resistance and water resistance. It can produce colors in a wide visible range, has excellent ozone resistance, light resistance and water resistance! It is possible to obtain excellent colored materials (recorded materials, etc.).
- the compounds of the above formula (1) synthesized in the examples are all mixtures, and unless otherwise specified, the positional isomer of the nitrogen-containing heteroaromatic ring and the positional isomer of the nitrogen atom of the nitrogen-containing heteroaromatic ring, unless otherwise specified.
- compounds having different ratios of the benzo ring Z nitrogen-containing heteroaromatic ring corresponding to A to D in the formula (1) and a Z j8 positional isomer of a substituted or unsubstituted sulfamoyl group in the benzo ring are included. .
- ⁇ max of the synthetic compound was measured by the following method.
- UV-2100 manufactured by Shimadzu Corporation
- the compound measured in pyridine is a reference value because the difference in solubility in the solvent is extremely low.
- a mixture of copper tribenzo (2,3-pyrido) porphyrazine and copper dibenzobis (2,3-pyrido) borfylazine (a mixture containing both in an equimolar ratio;
- the total amount of the obtained wet cake was added to 500 parts of 5% hydrochloric acid, the temperature was raised to 60 ° C., and the temperature was maintained for 1 hour.
- the crystals were filtered and washed with 200 parts of water.
- the entire amount of the obtained wet cake was added to 500 parts of 10% aqueous ammonia, the temperature of the solution was raised to 60 ° C., and the temperature was maintained at that temperature for 1 hour, and then the crystals were separated by filtration.
- the obtained crystals were washed 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 a mixture of copper tribenzo (2,3-pyrido) porphyrazine and copper dibenzobis (2,3-pyrido) porphyrazine 19. 8 parts as blue crystals It was.
- the precipitated crystals were separated by filtration to obtain 138.2 parts of a wet cake.
- the obtained wet cake was added to 500 parts of water and dissolved as ⁇ 0 using a 10% aqueous sodium hydroxide solution. At this time, the liquid volume was 700 parts. Concentrated hydrochloric acid was added to this solution to adjust the pH to 1.0, and 140 parts of sodium chloride sodium salt was added thereto over 20 minutes, followed by stirring for 20 minutes.
- the precipitated crystals were separated by filtration to obtain 160.0 parts of a wet cake.
- the obtained wet cake was added to a mixed liquid of 1250 parts of methanol and 125 parts of water, and the obtained liquid was stirred at 50 ° C. for 1 hour, filtered, and the separated crystals were washed with methanol. Wet cake 104. 8 parts were obtained.
- the obtained wet cake was dried to obtain 64.3 parts of the compound of the formula (12) as a white powder.
- the temperature of the solution was raised to 20 ° C over 10 minutes, and the reaction was carried out at the same temperature for 8 hours.
- the liquid volume at this time was 800 parts.
- the resulting reaction solution was heated to 50 ° C., 160 parts of sodium chloride sodium salt was added thereto, the solution was stirred for 10 minutes, and then adjusted to pH 1.0 with concentrated hydrochloric acid over 5 minutes.
- the precipitated crystals were separated by filtration to obtain 85.2 parts of a wet cake. Water is added to 85.2 parts of the obtained wet cake to make a liquid volume of 520 parts, the liquid temperature is raised to 50 ° C, and the pH is adjusted to 10.0 with 25% sodium hydroxide sodium hydroxide solution. The wet cake was completely dissolved.
- the precipitated crystals were separated by filtration to obtain 236.2 parts of a wet cake.
- the obtained wet cake was added to 1250 parts of methanol, 125 parts of water was further added thereto, and the resulting liquid was stirred at 50 ° C. for 1 hour and then filtered.
- the obtained wet cake was dried to obtain 58.4 parts of a compound of the above formula (14) as a white powder.
- the resulting solution was stirred overnight at room temperature, and then the pH was adjusted to 1 using concentrated hydrochloric acid.
- salt praying with sodium chloride (20% to the liquid) was performed, and the precipitate was separated by filtration to obtain 104 parts of a wet cake.
- the obtained wet cake was put into a beaker, 400 parts of water was added, and the obtained cake was dissolved using a 13% aqueous solution of sodium hydroxide and sodium chloride at a pH of 8.
- concentrated hydrochloric acid was used to adjust the pH of the obtained liquid to 1, and then salted with sodium chloride sodium salt (20% to the liquid), the precipitate was separated by filtration to obtain 16 parts of a wet cake 1 .
- the obtained wet cake was added to 300 parts of methanol, and then 30 parts of water was added thereto. The resulting suspension was stirred at 50 ° C. for 1 hour and then filtered to obtain 73 parts of a wet cake. The obtained wet cake was dried to obtain 45.7 parts of a compound of the above formula (16) as a white powder.
- the reaction was carried out at the same temperature for 8 hours. Next, after adjusting the temperature to 60 ° C, salting out with sodium chloride (20% to the liquid), 85 parts of the wet cake was added. Obtained.
- the obtained wet cake was put into a beaker, and 300 parts of water was added thereto, and the pH of the solution was adjusted to 11 using a 13% aqueous sodium hydroxide solution to dissolve the wet cake.
- the pH of the solution was adjusted to 1 with concentrated hydrochloric acid, and salted out with sodium chloride sodium chloride (20% to the solution), and the precipitate was separated by filtration to obtain 83 parts of a wet cake.
- Add the obtained wet cake to 300 parts of methanol, then add 30 parts of water, stir at 60 ° C for 1 hour, filter, wash with methanol and dry to obtain 14.5 parts of blue powder. It was.
- Cyanuric chloride 18.5 parts, Lecoal " ⁇ Ding 0-90 (trade name, surfactant, manufactured by Lion Corporation) 0.02 parts, 100 parts ice and 50 parts water in a beaker The mixture was stirred for 30 minutes at a temperature not higher than 10 ° C. Next, 41.9 parts of 6-aminonaphthalene-2-sulfonic acid (purity 53.3%) was added thereto, and then 13% sodium hydroxide aqueous solution When the pH of the liquid obtained using the solution was adjusted to 3 to 4, the liquid was stirred for 3 hours at 10 ° C. or lower, and 4-aminobenzenesulfonic acid (purity 99.0%) 17.
- the wet cake thus obtained was added to 400 parts of methanol, and then 40 parts of water was added thereto.
- the pH of the suspension was adjusted to 4 using 13% aqueous sodium hydroxide solution, and the suspension was stirred at 60 ° C. for 1 hour and then filtered.
- the obtained wet cake was dried to obtain 22.36 parts of a blue powder.
- the obtained wet cake was put into a beaker, 450 parts of water was added thereto, and a 13% aqueous sodium hydroxide solution was used to adjust the pH of the solution to 7 to dissolve the wet cake.
- the pH of the solution was adjusted to 1 with concentrated hydrochloric acid, and salted with sodium chloride sodium chloride (20% to the solution), and the precipitate was separated by filtration to obtain 140 parts of a wet cake.
- the obtained wet cake was added to 300 parts of methanol, and then 30 parts of water was added thereto, and the resulting liquid was stirred at 50 ° C. for 1 hour and then filtered to obtain 85 parts of a wet cake.
- the obtained wet cake was dried to obtain 61.7 parts of a white solid.
- the solution was stirred at room temperature for 3 hours. Next, 100 parts of ice was added thereto, the temperature of the solution was adjusted to 0 to 5 ° C., and then 60 parts of ethylenediamine was occasionally added. The resulting solution was stirred overnight at room temperature, and then the pH of the solution was adjusted to 1 using concentrated hydrochloric acid. After stirring for a while, the salt was prayed with sodium chloride (20% to the liquid), and the precipitate was separated by filtration to obtain 156 parts of a wet cake. Place the obtained wet cake in a beaker, add 450 parts of water to it, dissolve the wet cake with 13% aqueous solution of sodium hydroxide and sodium chloride at pH 11.5. It was.
- the pH of the solution obtained using concentrated hydrochloric acid was adjusted to 1, and then salted out with sodium chloride, and the precipitate was separated by filtration to obtain 180 parts of a wet cake.
- the obtained wet cake was placed in 400 parts of methanol, then added to water 40 and stirred at 50 ° C. for 1 hour to obtain a suspension.
- the suspension was filtered to obtain 104 parts of a wet cake.
- the obtained wet cake was dried to obtain 75.3 parts of a white solid.
- the temperature of the solution was raised to 20 ° C over 10 minutes, and the reaction was carried out at the same temperature for 8 hours.
- the liquid volume at this time was 600 parts.
- the resulting reaction solution was heated to 50 ° C., and 120 parts of sodium chloride salt was stirred there for 10 minutes, and then the pH of the solution was adjusted to 1.0 with hydrochloric acid over 5 minutes. Thereafter, the liquid was filtered to obtain 76.3 parts of a wet cake. Water was added to 76.3 parts of the obtained wet cake, the liquid volume was adjusted to 400 parts, the liquid temperature was raised to 55 ° C, and the liquid was added with 25% sodium hydroxide solution. The pH was adjusted to 8.0 to completely dissolve the wet cake.
- Trisodium salt of the following formula (24) (compound in which X in formula (4) is 2,5-disulfo-lino group, Y is 2-carboxy-4-sulfo-lino group, E is ethylene) Composition ( twenty four;
- Leocol RTM TD-90 (trade name, surfactant, manufactured by Lion Co., Ltd.) 0.09 part and 18.5 parts of salt water cyanurin were added to 100 parts of ice water, and the resulting solution was stirred for 30 minutes. did. Next, 39.9 parts of alin-2,5-disulfonic acid monosodium salt (purity 90.5%) was added thereto, and the pH of the liquid obtained while adding a 25% aqueous solution of sodium hydroxide and sodium carbonate was added. Was maintained at 2.7 to 3.0, and the reaction was carried out at 10 to 15 ° C for 1 hour and at 27 to 30 ° C for 2 hours.
- the liquid temperature was raised to 60 ° C., 340 parts of sodium chloride salt was added thereto to precipitate crystals, and concentrated hydrochloric acid was added to adjust the pH to 6.0.
- the precipitated crystals were separated by filtration and washed with 500 parts of a 20% sodium chloride aqueous solution.
- the total amount of the obtained crystals (aqueous wet cake) was added to 800 parts of water, and 25% aqueous sodium hydroxide solution was added to adjust the pH to 11. Further, water was added to adjust the liquid volume to 1000 parts, and the liquid temperature was raised to 60 ° C. Thereto was added 200 parts of sodium chloride salt, and the precipitated crystals were separated by filtration and washed with 500 parts of a 20% aqueous sodium chloride solution.
- the total amount of the obtained crystals (aqueous wet cake) was added to a mixed solution of 530 parts of methanol and 27 parts of water, and stirred at 60 ° C. for 1 hour to suspend.
- the crystals were separated by filtration, washed with 200 parts of methanol and dried to obtain 53.1 parts as a white powder.
- Example 1 Copper tribenzo (2,3 pyrido) porphyrazine trisulfuryl chloride and copper dibenzobis (2,3 pyrido) porphyrazine dihydrate obtained in the same manner as in Example 1- (2) in 100 parts of ice 40.0 parts of a wet cake of a mixture of sulfochloride was added, water was added to adjust the liquid volume to 400 parts, and the resulting liquid was stirred at 5 ° C. or lower for 15 minutes to obtain a suspension. A solution prepared by dissolving 13.4 parts of the compound of the formula (24) obtained in the above (1) in 100 parts of warm water was added to the suspension. After the addition, the pH was adjusted to 9.0 with 28% aqueous ammonia.
- the temperature was raised to 60 ° C, 80 parts of sodium chloride sodium salt was added, and the mixture was stirred for 5 minutes, and then adjusted to pH 1 with concentrated hydrochloric acid to precipitate crystals.
- the crystals were separated by filtration and washed with 200 parts of a 20% aqueous sodium chloride salt solution to obtain 74.9 parts of a wet cake.
- Leocol RTM TD-90 (trade name, surfactant, manufactured by Lion Co., Ltd.) 0.05 part and 9.2 parts of cyanuric chloride were added to 50 parts of ice water and stirred for 30 minutes.
- 29.9 parts of 6-aminonaphthalene-1,3-disulfonic acid (purity 72.5%) and adjust the pH 2.7 to 3.0 while adding 25% aqueous sodium hydroxide solution.
- the reaction was carried out at 8-10 ° C for 1 hour.
- 29.9 parts of 6-aminonaphthalene 1,3-disulfonic acid (purity 72.5%) and add 25% aqueous sodium hydroxide solution to maintain a pH of 6.0 to 8.0.
- reaction was carried out at 8-10 ° C for 4 hours, at 20 ° C for 1 hour, and at 60 ° C for 30 minutes. Thereafter, the temperature was maintained at 60 ° C, 60 parts of ethylenediamine was added all at once, the heating was stopped, and the mixture was stirred overnight. The temperature of the reaction solution was raised to 60 ° C, and concentrated hydrochloric acid was added to adjust the pH to 1.0. The liquid volume at this time was 600 parts. 120 parts of sodium chloride sodium salt was added, unnecessary substances were removed by filtration, and the obtained filtrate was concentrated under reduced pressure. 200 parts of water was added to the obtained residue. Thereto, 25% sodium hydroxide was added, the pH was adjusted to 11.5, and the residue was completely dissolved.
- Example 1 Copper tribenzo (2,3-pyrido) borfilazine trisulfuryl chloride and copper dibenzobis (2,3-pyrido) porphy obtained in the same manner as in Example 1- (2) in 50 parts of ice Add 40.0 parts of wet cake of the mixture of rosin disulfol chloride, add water, adjust the volume to 300 parts, and stir the resulting liquid at 5 ° C or lower for 15 minutes. A suspension was obtained. A solution obtained by dissolving 16.6 parts of the compound of the formula (26) obtained in the above (1) in 100 parts of warm water was added to the suspension. After the addition, the pH was adjusted to 9.0 with 28% aqueous ammonia.
- the temperature of the solution was raised to 20 ° C, and the reaction was carried out by holding at the same temperature for 5 hours.
- the liquid volume at this time was 560 parts.
- the resulting reaction solution was heated to 60 ° C., 112 parts of sodium chloride sodium salt was added thereto and stirred for 5 minutes, and then the pH was adjusted to 1.0 with concentrated hydrochloric acid to precipitate crystals.
- the crystals were separated by filtration and washed with 200 parts of a 20% aqueous sodium chloride solution to obtain 15.4 parts of a wet cake. Water was added to 15.4 parts of the obtained wet cake to adjust the liquid volume to 400 parts.
- the pH of the solution was adjusted to 8.2 with a 25% sodium hydroxide sodium solution to completely dissolve the wet cake.
- the liquid temperature was raised to 60 ° C., 80 parts of sodium chloride was added thereto, and the mixture was stirred for 5 minutes, adjusted to pH 1.0 with concentrated hydrochloric acid, and crystals were precipitated.
- the crystals were separated by filtration and washed with 200 parts of a 20% aqueous sodium chloride solution to obtain 16.9 parts of a wet cake. 16.9 parts of the obtained wet cake was added to a mixed solution of 100 parts of methanol and 5 parts of water, and stirred at 60 ° C. for 1 hour to be suspended.
- the suspended crystals were separated by filtration, washed with 100 parts of methanol and dried to obtain 3.7 parts of a blue powder.
- Formula (23) (mixture of No. 21, No. 22, and No. 23 in Table 2: A in formula (1), A, B, C, D 1.5 is fused at the 2nd and 3rd positions. The remaining 2.5 pyridine rings are benzene rings.
- Example 1 Copper tribenzo (2,3-pyrido) borfilazine trisulfuryl chloride and copper dibenzobis (2,3-pyrido) porphyra obtained in the same manner as in Example 1- (2) on 100 parts of ice 40.0 parts of a wet cake of a mixture of gindisulfol chloride was added, water was added, the liquid volume was adjusted to 400 parts, and the mixture was stirred at 5 ° C or lower for 15 minutes to obtain a suspension.
- Example 6 A solution of 77 parts of the compound of the formula (22) obtained in (1) dissolved in 100 parts of warm water and 3 parts of 28% aqueous ammonia was added to the suspension.
- the pH was adjusted to 9.0 with 28% aqueous ammonia. While maintaining the same pH, the liquid temperature was raised to 20 ° C. over 10 minutes, and the liquid was maintained at the same temperature for 8 hours to carry out the reaction. The liquid volume at this time was 500 parts.
- the resulting reaction solution was heated to 50 ° C., and 100 parts of sodium chloride sodium salt was stirred there for 10 minutes, and then the pH of the solution obtained with hydrochloric acid was adjusted to 1.0 over 5 minutes. Then, the precipitate was separated by filtration to obtain 41.2 parts of a wet cake. Water was added to 41.2 parts of the obtained wet cake to make a liquid volume of 400 parts.
- the liquid temperature was raised to 55 ° C., and the pH of the liquid was adjusted to 8.0 with a 25% sodium hydroxide solution to completely dissolve the wet cake. Then, 80 parts of sodium chloride salt was added and stirred for 15 minutes, and then the pH of the solution was adjusted to 4.0 with hydrochloric acid over 5 minutes. 43. Two parts were obtained. 43.2 parts of the obtained wet cake was added to 360 parts of methanol, 40 parts of water was added, and the mixture was stirred at 50 ° C. for 1 hour, filtered, and the resulting wet cake was washed with methanol, dried and dried. 8. 7 parts (sodium salt) of powder were obtained.
- the total amount of the obtained wet cake was placed in 500 parts of 5% hydrochloric acid, the liquid temperature was raised to 60 ° C., and the temperature was maintained for 1 hour. The crystals were separated by filtration and washed with 200 parts of water. Next, the entire amount of the obtained wet cake was placed in 500 parts of 10% aqueous ammonia, held at 60 ° C for 1 hour, the crystals were separated by filtration, washed with 300 parts of water, and then with 100 parts of methanol. 33. 6 parts were obtained. The obtained wet cake was dried at 80 ° C. to obtain 20.0 parts of copper tribenzo (2,3-pyrido) borfilazine as blue crystals.
- reaction solution is cooled to 30 ° C or lower, slowly poured into 800 parts of ice water, the precipitated crystals are separated by filtration, washed with 200 parts of cold water, and copper tribenzo (2,3-pyrido) vorfilazine. 40.1 parts of a trisulfol chloride wet cake were obtained.
- Example 6 A solution prepared by dissolving 4.77 parts of the compound of the formula (22) obtained in (1) with 100 parts of warm water and 3 parts of 28% aqueous ammonia was added to the suspension. After the addition, the pH of the liquid obtained with 28% aqueous ammonia was adjusted to 9.0.
- Formula (23) (mixture of No. 21, No. 22, and No. 23 in Table 2: A in formula (1), A, B, C, D 1.5 is fused at the 2nd and 3rd positions. Of the pyridine ring and the remaining 2.5 is a benzene ring, X is a 4-sulfoa-lino group, Y is a 3-sulfoa-lino group, and E is ethylene).
- Example 6 To 100 parts of ice, add 40.1 parts of the wet cake of copper tribenzo (2,3 pyrido) borfirazine trisulfol chloride obtained in Example 10- (2), and add water thereto. The liquid volume was adjusted to 400 parts and stirred at 5 ° C. or lower for 15 minutes to obtain a suspension.
- Example 6 A solution of 77 parts of the compound of formula (22) obtained in (1) dissolved in 100 parts of warm water and 3 parts of 28% aqueous ammonia was added to the suspension. After the addition, the solution was adjusted to pH 9.0 with 28% aqueous ammonia. While maintaining the same pH, the temperature was raised to 20 ° C. over 10 minutes, and the reaction was carried out at the same temperature for 8 hours.
- the liquid volume at this time was 600 parts.
- the temperature of the resulting reaction solution was raised to 50 ° C., 120 parts of salt ammonium was added thereto, stirred for 10 minutes, and then the pH of the solution obtained with hydrochloric acid over 5 minutes was adjusted. The pH was adjusted to 1.0, and the precipitated crystals were separated by filtration to obtain 46.2 parts of a wet cake. 46.2 parts of the obtained wet cake was added to 360 parts of methanol, 40 parts of water was stirred at 50 ° C for 1 hour, filtered, and the resulting wet cake was washed with methanol and dried. 10.6 parts (ammonium salt) of blue powder were obtained.
- Butinorecanorebitonore 2. 0 parts
- Butinorecanorebitonore 2. 0 parts
- an inkjet recording dye generally used as CI Direct Blue 199, product name: Projet Cyan 1 (manufactured by Avecia: Comparative Example 1), and Example of Patent Document 8 Printing using the dye mixture synthesized and purified by the method described in 1 (Comparative Example 2) and the dye compound synthesized and purified by the method described in Example 3 of Patent Document 12 (Comparative Example 3)
- a comparative ink was prepared in the same manner as the ink preparation described in (A) above so that the printing density was the same as the inks of Examples 1 to 10 in Table 2.
- the dye of Comparative Example 1 The ink used was C-A, the ink using the pigment of Comparative Example 2 was C-B, and the ink using the pigment of Comparative Example 3 was CC.
- yellow ink was prepared with C. I. Direct Yellow 132 V as the yellow dye and the composition shown in Table 4 below.
- Butinorecanorebitonore 2. 0 parts
- a magenta ink having the composition shown in Table 5 below was prepared using the dye described in 3, ie, the dye represented by the following formula (103).
- Butinorecanorebitonore 2. 0 parts
- Glossy paper A Advanced Photo Paper (Glossy) Q78 71A) manufactured by Hewlett-Packard Japan Ltd.
- Glossy Paper B Seiko Epson Co., Ltd. photographic paper
- PIXUS ip3100 manufactured by Canon Inc. Inkjet recording was performed on two types of KA420PSK.
- an image pattern was created to obtain 6 levels of gradation of 100%, 85%, 70%, 55%, 40%, and 25% with a single cyan color, and a halftone print was obtained. .
- Resistance In the light test and the ozone resistance test, the reflection density D value of the printed material before the test was closest to 1.0 V, and the measurement was performed using the gradation portion.
- the print of the mixed color part is a yellow color and a green pattern, and the magenta color is a blue pattern.
- the density is 100%, 85%, 70%, 55%, 40, respectively.
- Image patterns were created so that 6 gradations of% and 25% were obtained.
- the hue of the recorded image was measured using a colorimetric system (SectroEye: manufactured by GretagMacbeth) and the a * and b * values when the L * of the printed material was in the range of 40 to 80 were measured. .
- the evaluation was carried out in three stages, with the preferred a * value defined as -60 to -20 and the b * value defined as -60 to -20.
- the C * value was compared and evaluated for the mixed color portion of the cyan ink and yellow ink of the present invention or the cyan ink and magenta ink of the present invention.
- the green color that is, the hue (green)
- the L * value of the printed material in the range of 54 to 62, and depending on the C * value there are the following three levels. It was evaluated with.
- the blue color which is the color mixture with magenta ink, that is, the hue (blue)
- the measurement is performed in the portion where the L * value of the printed material is in the range of 37 to 43, and the following C * value determines the following. Evaluation was made in three stages.
- C * value is 63 or more ⁇ : C * value less than 63 60 or more
- the test piece of the recorded image was irradiated with a xenon weather meter (ATLAS model Ci4000) at 0.36 WZ square meter illuminance for 50 hours under the conditions of a bath temperature of 24 ° C and humidity of 60% RH.
- the reflection density before and after the test was measured using a colorimetric system when the reflection density (D value) was in the range of 0.70 to 0.85.
- the residual ratio of the dye was calculated by (reflection density after test Z reflection density before test) X 100 (%) and evaluated in three stages.
- test piece of the recorded image is placed on an ozone weather meter (model OM made by Suga Test Instruments Co., Ltd.
- ⁇ Residual rate less than 85%, 70% or more
- the specimen of the recorded image was left for 3 days at a temperature of 50 ° C and a humidity of 90% RH using a constant temperature and humidity chamber (Applied Giken Sangyo Co., Ltd.). After the test, the bleeding of the test piece was visually evaluated in three stages.
- the cyan ink using the compound of the present invention showed a good hue without changing whether it was a single color or a mixed color.
- the C * values of C-A, C-B, and C-C which are the inks of the comparative examples, are respectively C when glossy paper ⁇ is used.
- — A and C— C is less than 60 and C—B is less than 63 and more than 60, whereas C-1 to C-8, which are inks of the present invention, have a C * value of 63 or more in any case.
- the C * values of C-A, CB, and C-C, which are the inks of the comparative examples, are less than 63 for CA and CB, respectively 60 or more, and 60 for C-C. While it is full, it is C / C 12! The value is 63 or more, indicating that the saturation is higher than that of each ink of the comparative example.
- the residual ratio of the dye before and after the test of CA and CB, which are comparative examples, is less than 50%.
- ⁇ C 12! / In the case of deviation, even in the case of deviation! Even at the lowest value, the pigment retention rate is 70% or more, and it has excellent ozone resistance. I understand.
- the ink using the coloring matter of the present invention can broaden the color reproduction range of the printed matter as compared with the ink of the comparative example, and is excellent in light resistance, ozone resistance and moisture resistance.
- ozone resistance is very good.
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- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
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- Inks, Pencil-Leads, Or Crayons (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Ink Jet (AREA)
Description
Claims
Priority Applications (6)
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KR1020087023927A KR101321889B1 (ko) | 2006-04-07 | 2007-04-05 | 포르피라진 색소, 잉크, 잉크세트 및 착색체 |
CA 2648734 CA2648734C (en) | 2006-04-07 | 2007-04-05 | Porphyrazine coloring matter, ink, ink set and colored product |
EP20070741087 EP2017309B1 (en) | 2006-04-07 | 2007-04-05 | Porphyrazine dye, ink, ink set, and colored matter |
US12/226,043 US7585361B2 (en) | 2006-04-07 | 2007-04-05 | Porphyrazine coloring matter, ink, ink set and colored product |
CN2007800125876A CN101415782B (zh) | 2006-04-07 | 2007-04-05 | 四氮杂卟啉色素、油墨、油墨组及着色体 |
JP2008509872A JP5066079B2 (ja) | 2006-04-07 | 2007-04-05 | ポルフィラジン色素、インク、インクセット及び着色体 |
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US (1) | US7585361B2 (ja) |
EP (1) | EP2017309B1 (ja) |
JP (1) | JP5066079B2 (ja) |
KR (1) | KR101321889B1 (ja) |
CN (1) | CN101415782B (ja) |
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Also Published As
Publication number | Publication date |
---|---|
KR20080109790A (ko) | 2008-12-17 |
TW200804531A (en) | 2008-01-16 |
US20090151599A1 (en) | 2009-06-18 |
TWI396720B (zh) | 2013-05-21 |
CA2648734C (en) | 2013-01-15 |
CA2648734A1 (en) | 2007-10-18 |
JPWO2007116933A1 (ja) | 2009-08-20 |
CN101415782B (zh) | 2012-12-12 |
EP2017309A4 (en) | 2010-08-11 |
KR101321889B1 (ko) | 2013-10-25 |
EP2017309B1 (en) | 2011-10-05 |
CN101415782A (zh) | 2009-04-22 |
JP5066079B2 (ja) | 2012-11-07 |
EP2017309A1 (en) | 2009-01-21 |
US7585361B2 (en) | 2009-09-08 |
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