Classifications

• • 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
• • 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
  • 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
  • C09B47/22—Obtaining compounds having nitrogen atoms directly bound to the phthalocyanine skeleton
• • 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

Definitions

• the present invention relates to a coloring composition, an ink for inkjet recording, an inkjet recording method, and a phthalocyanine compound.
• the inkjet recording method is a method of printing by flying small droplets of ink for inkjet recording and adhering them to a recording medium such as paper.
• This printing method can print high-resolution, high-quality images at high speed and easily with an inexpensive device.
• Patent Document 1 describes an ink for inkjet recording using a phthalocyanine compound having an alkylsulfonyl group substituted with a sulfo group as a substituent as a dye.
• a solvent is added to a coloring composition (also referred to as "conc ink") having a high dye content (for example, a dye content of 6 to 15% by mass) to adjust the dye concentration for inkjet recording.
• Inks may be produced, but with conventional coloring compositions, the pH may fluctuate when stored for a long time in the state of solvent ink, and improvement is required.
• An object of the present invention is a coloring composition having excellent fastness to ozone gas and excellent storage stability when used as a conch ink, an inkjet recording ink containing the coloring composition, and an inkjet recording method using the inkjet recording ink. , And a phthalocyanine compound that can be used as a dye in the above coloring composition.
• a coloring composition containing a phthalocyanine compound represented by the following general formula (1) A coloring composition containing a phthalocyanine compound represented by the following general formula (1).
• R 1 to R 8 independently represent a hydrogen atom or a nitro group.
• x represents a nitro group.
• Q 1 ⁇ Q 8 each independently represent a hydrogen atom or a -SO 2 -Z 1.
• 4- x number represents -SO 2 -Z 1.
• Z 1 represents an alkyl group substituted with a sulfo group, an aryl group substituted with a sulfo group, or a heterocyclic group substituted with a sulfo group. If Z 1 there are a plurality, a plurality of Z 1 may be the same or different.
• x represents a number from 1 to 4.
• M represents a hydrogen atom or a metal element.
• Z 1 represents an alkyl group substituted with a sulfo group.
• x represents a number of 1 to 2.
• ⁇ 4> The coloring composition according to any one of ⁇ 1> to ⁇ 3>, wherein the content of the phthalocyanine compound represented by the general formula (1) is 6 to 15% by mass.
• ⁇ 5> An inkjet recording ink containing the coloring composition according to any one of ⁇ 1> to ⁇ 4>.
• ⁇ 6> An inkjet recording method using the inkjet recording ink according to ⁇ 5>.
• R 1 to R 8 independently represent a hydrogen atom or a nitro group.
• x represents a nitro group.
• Q 1 ⁇ Q 8 each independently represent a hydrogen atom or a -SO 2 -Z 1.
• 4- x number represents -SO 2 -Z 1.
• Z 1 represents an alkyl group substituted with a sulfo group, an aryl group substituted with a sulfo group, or a heterocyclic group substituted with a sulfo group. If Z 1 there are a plurality, a plurality of Z 1 may be the same or different.
• x represents a number from 1 to 4.
• M represents a hydrogen atom or a metal element.
• a coloring composition having excellent fastness to ozone gas and excellent storage stability when used as a conch ink, an inkjet recording ink containing the coloring composition, and an inkjet recording method using the inkjet recording ink.
• a phthalocyanine compound that can be used as a dye in the above coloring composition can be provided.
• the coloring composition of the present invention contains a phthalocyanine compound represented by the following general formula (1).
• R 1 to R 8 independently represent a hydrogen atom or a nitro group.
• x represents a nitro group.
• Q 1 ⁇ Q 8 each independently represent a hydrogen atom or a -SO 2 -Z 1.
• 4- x number represents -SO 2 -Z 1.
• Z 1 represents an alkyl group substituted with a sulfo group, an aryl group substituted with a sulfo group, or a heterocyclic group substituted with a sulfo group. If Z 1 there are a plurality, a plurality of Z 1 may be the same or different.
• x represents a number from 1 to 4.
• M represents a hydrogen atom or a metal element.
• the present invention also relates to a phthalocyanine compound represented by the above general formula (1).
• Phthalocyanine compound represented by the general formula (1) is, Q 1 in the phthalocyanine skeleton ⁇ -position (formula (1) in the R 1 ⁇ R 8) x number of nitro groups to, beta-position (formula (1) the ⁇ Q 8) is a phthalocyanine compound having a 4-x-number of -SO 2 -Z 1. However, x represents a number from 1 to 4.
• x in the general formula (1) may be a value for one kind of compound or an average value for a mixture containing a plurality of kinds of compounds. That is, the phthalocyanine compound represented by the general formula (1) may represent a compound of one kind alone, or may represent a mixture containing two or more kinds of compounds. The mixture may be a mixture of all phthalocyanine compounds that may be obtained during the synthesis of the phthalocyanine compound, or may be a mixture of some of the phthalocyanine compounds. Further, it may be a mixture containing a specific phthalocyanine compound in a specific mixing ratio.
• each phthalocyanine compound constituting the mixture may include those that do not satisfy the requirement of x in the general formula (1). .. Specifically, for example, -SO 2 -Z 1 group may include four substituted phthalocyanine compound.
• the phthalocyanine compound represented by the general formula (1) has a nitro group having a high electron attracting property at a specific position ( ⁇ -position), so that the HOMO (Highest Occupied Molecular Orbital) of the phthalocyanine compound is the highest occupied orbital. Since the level can be stabilized and the reactivity with ozone gas can be reduced, it is presumed that the robustness to ozone gas is excellent. Furthermore, the phthalocyanine compound represented by the general formula (1) also has, surprisingly, high storage stability as a conquin ink.
• the phthalocyanine compound represented by the general formula (1) of the present invention is typically a mixture, and therefore, for example, when stored as a 6 to 15 mass% aqueous solution.
• the association between individual phthalocyanine compounds is suppressed, and the sulfo group in the phthalocyanine compound can exist alone in the aqueous solution.
• changes in the association state are suppressed even when the ink is stored as a conquer ink, so that it is presumed that the pH fluctuation is small and stable storage is possible.
• the phthalocyanine compound represented by the general formula (1) of the present invention includes a compound, a salt thereof, and a hydrate thereof.
• Z 1 represents an alkyl group substituted with a sulfo group, an aryl group substituted with a sulfo group, or a heterocyclic group substituted with a sulfo group. If Z 1 there are a plurality, a plurality of Z 1 may be the same or different.
• Examples of the alkyl group when Z 1 represents an alkyl group substituted with a sulfo group include, for example, a linear or branched alkyl group, and specifically, a methyl group, an ethyl group, an n-propyl group, and the like. Examples thereof include i-propyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group and n-heptyl group.
• the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, further preferably an alkyl group having 3 carbon atoms, and n ⁇ . It is particularly preferably a propyl group.
• the number of sulfo groups substituted with the above alkyl groups is not particularly limited, but is preferably 1 to 3, more preferably 1 to 2, and even more preferably 1.
• Examples of the aryl group when Z 1 represents an aryl group substituted with a sulfo group include a phenyl group and a naphthyl group.
• the aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms, and further preferably a phenyl group.
• the number of sulfo groups substituted with the above aryl groups is not particularly limited, but is preferably 1 to 3, more preferably 1 to 2, and even more preferably 1.
• heterocyclic group in the case where Z 1 represents a heterocyclic group substituted with a sulfo group include an aromatic or non-aromatic heterocyclic group, and a 5- or 6-membered aromatic heterocyclic group is used.
• aromatic or non-aromatic heterocyclic group Preferably, for example, 1,3,4-thiasiazol-2-yl group, pyridyl group, imidazolyl group, thienyl group and the like can be mentioned.
• the heterocyclic group is preferably a heterocyclic group having 2 to 9 carbon atoms, more preferably a heterocyclic group having 2 to 5 carbon atoms, and is a 1,3,4-thiadiazole-2-yl group.
• a pyridyl group is more preferred, and a 1,3,4-thiadiazole-2-yl group is particularly preferred.
• the number of sulfo groups substituted with the heterocyclic group is not particularly limited, but is preferably 1 to 3, more preferably 1 to 2, and even more preferably 1.
• Z 1 is preferably an alkyl group substituted with a sulfo group, and more preferably an alkyl group having 1 to 10 carbon atoms substituted with a sulfo group. It is more preferably an alkyl group having 1 to 5 carbon atoms substituted with a sulfo group, particularly preferably an alkyl group having 3 carbon atoms substituted with a sulfo group, and an n-propyl group substituted with a sulfo group. Is most preferable.
• the sulfo group contained in Z 1 may be in a salt state. That is, in the present invention, "sulfo group" is represented by -SO 3 M 1, M 1 represents a hydrogen atom or a cation.
• cations include ammonium ions, alkali metal ions (eg, lithium ions, sodium ions, potassium ions) and organic cations (eg, tetramethylammonium ions, tetramethylguanidium ions, tetramethylphosphoniums).
• alkali metal ions are preferable, and sodium ions and lithium ions are particularly preferable because they increase the solubility of the compound in an aqueous medium and improve the storage stability as a conch ink.
• X in the general formula (1) represents a number from 1 to 4.
• the phthalocyanine compound represented by the general formula (1) may represent a mixture, and x is the average number of nitro groups introduced into one phthalocyanine skeleton, and is not necessarily an integer. good.
• the number of x is more preferably 1 to 2 from the viewpoint of solubility and hue, and 1 is most preferable.
• M represents a hydrogen atom or a metal element.
• preferred Ms include Li, Na, K, Mg, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Ru, as metal elements.
• examples thereof include Rh, Pd, Os, Ir, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb and Bi.
• Cu, Ni, Zn, Al, or Mg is preferable, Cu or Mg is more preferable, and Cu is further preferable, from the viewpoint of fastness to ozone gas and hue.
• the phthalocyanine compound represented by the general formula (1) of the present invention is, for example, a dicarbonitrile derivative (general formula (a)) represented by the following formula and / or a 1,3-diiminoisoindoline derivative (general formula (general formula (a)). b)) can be induced by reacting with a metal derivative represented by the general formula (d).
• a phthalocyanine compound In the synthesis of a water-soluble substituted phthalocyanine compound, to give a method using those introduced nitro group or -SO 2 -Z 1 group in advance in the general formula (a) and / or formula (b) as a raw material, a phthalocyanine compound a method of water-solubilizing by introducing a nitro group or a -SO 2 -Z 1 group after.
• Ra 1 in the general formula (a) and Rb 1 in the general formula (b) correspond to R 1 , R 3 , R 5 and R 7 in the general formula (1)
• the general formula Ra 2 in (a) and Rb 2 in the general formula (b) correspond to R 2 , R 4 , R 6 and R 8 in the general formula (1)
• the general formula (a) Qa 1 in the general formula (b) and Qb 1 in the general formula (b) correspond to Q 1 , Q 3 , Q 5 , and Q 7 in the general formula (1)
• 2 and Qb 2 in the general formula (b) correspond to Q 2 , Q 4 , Q 6 and Q 8 in the general formula (1).
• the phthalocyanine compound represented by the general formula (1) at least one of an acid and a base can be used.
• the acid is not particularly limited, but any organic compound or inorganic compound is preferable as long as the dissociation index pKa in the aqueous solution at 25 ° C. is 7.0 or less.
• pKa represents the reciprocal logarithmic value of the acid dissociation constant, and represents the value obtained at an ionic strength of 0.1 and 25 ° C.
• the acid having a pKa of 0.0 to 7.0 may be any of an inorganic acid such as phosphoric acid and an organic acid such as acetic acid, malonic acid and citric acid.
• organic acids having a carboxyl group are most preferable.
• the organic acid having a pKa of 0.0 to 7.0 may be a monobasic organic acid or a polybasic organic acid.
• a polybasic organic acid if its pKa is in the above range of 0.0 to 7.0, it can be used as a metal salt (for example, sodium salt or potassium salt) or an ammonium salt.
• two or more kinds of organic acids having pKa of 0.0 to 7.0 can be mixed and used.
• Preferred specific examples of the organic acid having a pKa of 0.0 to 7.0 used in the present invention are formic acid, acetic acid, monochloroacetic acid, monobromoacetic acid, glycolic acid, propionic acid, monochloropropionic acid, lactic acid, pyruvate and acrylic acid.
• Amino acid compounds mono-substituted benzoic acids such as chloro and hydroxy, aromatic monobasic organic acids such as nicotinic acid; oxalic acid, malonic acid, succinic acid, tartaric acid, malic acid, maleic acid, fumaric acid, Aliphatic dibasic organic acids such as oxaloacetate, glutaric acid and adipic acid; amino acid dibasic organic acids such as aspartic acid, glutamic acid, glutaric acid, cystine and ascorbic acid; aromatics such as phthalic acid and terephthalic acid.
• Dibasic organic acids; various organic acids such as tribasic organic acids such as citric acid can be listed. In the present invention, among the organic acids, aliphatic monobasic organic acids are preferable, and formic acid, acetic acid, and propionic acid are most preferable.
• the amount of the compound having a pKa of 7.0 or less is the amount of the dicarbonitrile derivative represented by the above formula (general formula (a)) and / or the 1,3-diiminoisoindoline derivative (general formula (b)).
• the dicarbonitrile derivative represented by the above formula (general formula (a)) and / or 1 is charged in an amount of 0.05 to 20 equivalents, preferably 0.1 to 10 times the amount used.
• a decomposition inhibitory effect of the 3-diiminoisoindoline derivative (general formula (b)) can be obtained.
• the base used in this reaction is preferably an inorganic base or an organic base.
• the inorganic base include inorganic bases such as lithium carbonate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, lithium hydroxide and potassium hydroxide
• examples of the organic base include triethylamine, tributylamine, diisopropylethylamine, pyridine and dimethylamino. Pyridine and the like can be used.
• organic acid salts such as sodium acetate, lithium acetate, potassium acetate, ammonium acetate, sodium oxalate and ethylenediaminetetraacetic acid disodium salt can also be used.
• the amount of the base used is 0, based on the amount of the dicarbonitrile derivative represented by the above formula (general formula (a)) and / or the 1,3-diiminoisoindoline derivative (general formula (b)). It is 05 to 30.0 equivalents, preferably 0.5 to 15.0 equivalents.
• a buffer solution is a solution having a large buffering action against a change in the concentration of a certain component in the solution.
• a mixed solution of a weak acid (AH) such as acetic acid and its conjugate base (A ⁇ ) can slightly suppress the pH change even if a small amount of H + or OH ⁇ is added.
• Systems containing a weak base (B) and a conjugate acid (BH + ) show similar effects.
• a practical pH buffer solution it can be found in many general books, but for example, it is detailed in the 5th edition of "Physical and Chemical Dictionary” edited by Saburo Nagakura (Iwanami Shoten, 1999).
• a dicarbonitrile derivative represented by the above formula (general formula (a)) and / or a 1,3-diiminoisoindoline derivative (general formula (b)) and the above general formula It is desirable to react the metal derivative represented by (d) in the presence of at least one of the acid and the base having a pKa of 14.0 or less.
• the reaction temperature is 30. It is about 220 ° C., preferably 40 to 200 ° C., and more preferably 50 to 180 ° C.
• Examples of the metal derivative represented by the above general formula (d) to be added to the reaction of the present invention include metals and metal hydroxides for the metal or metal oxide to be introduced, as well as metal chlorides, metal acetates, and complexes. As, a metal aco complex and an ammine complex can be used.
• preferred Md includes a metal atom or an oxide, a hydroxide, and a halide thereof.
• Metal atoms include Li, Na, K, Mg, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu. , Ag, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi and the like.
• oxides examples include VO and Geo.
• hydroxide examples include Si (OH) 2 , Cr (OH) 2 , Sn (OH) 2, and the like.
• halide examples include AlCl, SiCl 2 , VCl, VCl 2 , VOCl, FeCl, GaCl, ZrCl and the like.
• the M d, Cu, Ni, Zn , Al, Mg and the like are preferable, Cu, Mg is the most preferred.
• Z d represents a halogen atom, acetate anion, acetyl acetonate, represents a monovalent or divalent ligand such as oxygen, n d represents an integer of 1-4.
• metal derivative ⁇ metal derivative represented by the general formula (d) ⁇ include Al, Si, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Ge, Ru, Rh, Pd, and In. , Sn, Pt, Pb and other halides, carboxylic acid derivatives, sulfates, nitrates, carbonyl compounds, oxides, complexes and the like.
• cupric chloride (CuCl 2 ) and copper acetate are particularly preferable, and copper chloride (CuCl 2 ) is particularly preferable.
• the amount used is 0, with respect to the amount of the dicarbonitrile derivative represented by the above formula (general formula (a)) and / or the 1,3-diiminoisoindoline derivative (general formula (b)).
• a 01 to 10 times equivalent is preferable, a 0.05 to 5 times equivalent is preferable, and a particularly preferable amount is a 0.1 to 3 times equivalent.
• the catalyst may be used at the same time.
• all catalysts usually used for synthesizing phthalocyanine compounds can be used, and examples thereof include molybdate compounds such as ammonium molybdate, molybdate, ammonium phosphate, molybdenum oxide, and tank steonic acid.
• molybdate compounds such as ammonium molybdate, molybdate, ammonium phosphate, molybdenum oxide, and tank steonic acid.
• tungsten compounds such as ammonium and ammonium phosphate, vanadium arsenide compounds, boric acid, and halides or oxyhalides of titanium, tin and antimony, and ammonium molybdate is particularly excellent.
• the solvent that can be used in the production of the phthalocyanine compound of the present invention is not particularly limited, and a general organic solvent can be used.
• organic solvents having a hydroxyl group and polar solvents eg, acetonitrile, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, sulfolane, propylene carbonate, N-methyl-2-pyrrolidone, N- Vinyl-2-pyrrolidone, N, N-diethyldodecaneamide
• polar solvents eg, acetonitrile, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, sulfolane, propylene carbonate, N-methyl-2-pyrrolidone, N- Vinyl-2-pyrrolidone, N, N-diethyldodecaneamide
• Examples of more preferred alcohols are methanol, ethanol, n-propanol, isopropanol, n-pentanol, n-heptanol, n-octanol, cyclohexanol, benzyl alcohol, phenethyl alcohol, phenylpropyl alcohol, furfuryl alcohol, anis alcohol.
• benzyl alcohol phenethyl alcohol, phenylpropyl alcohol, furfuryl alcohol, anis alcohol.
• Ethylene-based compounds are also advantageous.
• methanol, ethanol, isopropanol, ethylene glycol, 1,2- and 1,3-propylene glycol, diethylene glycol, tri- and tetraethylene glycol, di-, tri- and tetrapropylene glycol are preferable, and ethylene glycol is particularly preferable.
• Diethylene glycol is most preferred.
• an industrially used inert solvent can also be used.
• examples include nitrobenzene, trichlorobenzene, chloronaphthalene, methylnaphthalene, naphthalene, alkylbenzene, paraffin, naphthen and kerosene.
• the amount of the solvent used is 1 to 100 times by mass, preferably 1 to 100 times by mass, that of the dicarbonitrile derivative represented by the above formula (general formula (a)) and / or the 1,3-diiminoisoindoline derivative (general formula (b)). It is 1 to 20 times by mass, more preferably 1 to 5 times by mass.
• reaction time is preferably less than 96 hours, more preferably less than 48 hours, still more preferably less than 30 hours.
• the product (phthalocyanine compound) obtained by these reactions can be treated according to a post-treatment method of a normal organic synthesis reaction, and then purified or unpurified. ..
• reaction solvent is distilled off, or the reaction solvent is poured into water or ice without distilling off, and the liberated material is neutralized or unneutralized without purification or recrystallization. It can also be provided after performing the operation of purification by column chromatography or the like alone or in combination.
• reaction solvent is distilled off, or the reaction solvent is not distilled off, and the mixture is neutralized by pouring it into water or ice, or the extract is purified with an organic solvent / aqueous solution without neutralization. It can also be provided without, or after performing the operation of purification by crystallization or column chromatography alone or in combination.
• the coloring composition of the present invention contains a phthalocyanine compound represented by the above general formula (1).
• the type of the phthalocyanine compound represented by the general formula (1) contained in the coloring composition of the present invention may be one kind or two or more kinds.
• the coloring composition of the present invention can further contain a medium, but is particularly suitable as an ink for inkjet recording when a solvent is used as the medium.
• the coloring composition of the present invention can be prepared by using a lipophilic medium or an aqueous medium as a medium and dissolving and / or dispersing the compound represented by the general formula (1) in them. ..
• an aqueous medium is used.
• the aqueous medium will be described later.
• the coloring composition of the present invention also includes a composition for ink excluding the medium.
• the content of the compound represented by the general formula (1) contained in the coloring composition is not particularly limited, and the type of substituent in the compound represented by the general formula (1) used and the type of substituent and the compound represented by the general formula (1) used. It is determined by the type of solvent component used for producing the coloring composition and the like.
• the total content of the compounds represented by the general formula (1) in the coloring composition is 0.1 to 20 with respect to the total mass of the coloring composition. It is preferably by mass, more preferably 0.2 to 10% by mass, further preferably 1 to 10% by mass, and particularly preferably 2 to 6% by mass.
• the total content of the compounds represented by the general formula (1) contained in the coloring composition By setting the total content of the compounds represented by the general formula (1) contained in the coloring composition to 1% by mass or more, the printing density of the ink on the recording medium at the time of printing can be improved. Further, by setting the total content of the compounds represented by the general formula (1) contained in the coloring composition to 10% by mass or less, the ejection property of the coloring composition is improved when used in the inkjet recording method. In addition, the effect of preventing clogging of the inkjet nozzle can be obtained.
• the coloring composition of the present invention may be a conch ink containing 6 to 15% by mass of the compound represented by the general formula (1).
• the coloring composition of the present invention is also excellent in storage stability as a conquer ink, and even when stored as an aqueous solution containing 10% by mass of the compound represented by the general formula (1), the pH does not fluctuate and is stored. Excellent stability.
• the coloring composition of the present invention may contain other additives, if necessary, within a range that does not impair the effects of the present invention.
• other additives include additives that can be used in the ink for inkjet recording described later.
• the ink for inkjet recording of the present invention contains the above-mentioned coloring composition.
• the ink for inkjet recording can be produced by dissolving and / or dispersing the phthalocyanine compound represented by the above general formula (1) in a lipophilic medium or an aqueous medium. An ink using an aqueous medium is preferable.
• additives include, for example, anti-drying agents (wetting agents), anti-fading agents, emulsion stabilizers, penetration promoters, UV absorbers, preservatives, fungicides, pH regulators, surface tension regulators, defoamers.
• Known additives such as foaming agents, viscosity regulators, dispersants, dispersion stabilizers, rust preventives, chelating agents and the like can be mentioned.
• these various additives are added directly to the ink liquid.
• the oil-soluble dye is used in the form of a dispersion, it is generally added to the dispersion after preparation of the dye dispersion, but it may be added to the oil phase or the aqueous phase at the time of preparation.
• the anti-drying agent is preferably used for the purpose of preventing clogging due to drying of the ink for inkjet at the ink injection port of the nozzle used in the inkjet recording method.
• a water-soluble organic solvent having a lower vapor pressure than water is preferable.
• Specific examples include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivative, and glycerin.
• Polyhydric alcohols such as trimethylolpropane, lower alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl) ether.
• the penetration accelerator is preferably used for the purpose of allowing the inkjet ink to penetrate the paper better.
• alcohols such as ethanol, isopropanol, butanol, di (tri) ethylene glycol monobutyl ether and 1,2-hexanediol, sodium lauryl sulfate, sodium oleate, nonionic surfactant and the like can be used. .. If these are contained in the ink in an amount of 5 to 30% by mass, they usually have a sufficient effect, and it is preferable to use them in an amount of addition that does not cause print bleeding or paper omission (print through).
• Ultraviolet absorbers are used for the purpose of improving the storage stability of images.
• Examples of the ultraviolet absorber include benzotriazoles described in JP-A-58-185677, JP-A-61-190537, JP-A-2-782, JP-A-5-97075, JP-A-9-34057 and the like.
• JP-A-48-30492 JP-A-56-21141
• Triazole compounds described in JP-A-10-88106, etc. JP-A-4-298503, JP-A-8-53427, JP-A-8-239368, JP-A-10-182621, JP-A-8.
• a compound described in No. 24239, a compound that absorbs ultraviolet rays and emits fluorescence, such as a stilbene-based compound and a benzoxazole-based compound, a so-called fluorescent whitening agent can also be used.
• the anti-fading agent is used for the purpose of improving the storage stability of the image.
• various organic and metal complex-based anti-fading agents can be used.
• Organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indans, chromans, alkoxyanilines, heterocycles, etc., and nickel as a metal complex.
• the compounds described in the patent cited in 15162 and the compounds included in the general formulas and compound examples of the representative compounds described on pages 127 to 137 of JP-A-62-215272 can be used.
• fungicide examples include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one and salts thereof. These are preferably used in an ink in an amount of 0.02 to 1.00% by mass.
• a neutralizing agent (organic base, inorganic alkali) can be used as the pH adjusting agent.
• the above pH adjuster is preferably added so that the pH of the inkjet recording ink is 6 to 10, and more preferably 7 to 10 for the purpose of improving the storage stability of the inkjet recording ink. ..
• the surface tension adjusting agent examples include nonionic, cationic or anionic surfactants.
• the surface tension of the inkjet ink of the present invention is preferably 25 to 70 mN / m. Further, 25 to 60 mN / m is preferable.
• the viscosity of the inkjet recording ink of the present invention is preferably 30 mPa ⁇ s or less. Further, it is more preferable to adjust to 20 mPa ⁇ s or less.
• surfactants include fatty acid salts, alkyl sulfates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphates, naphthalene sulfonic acid formarin condensates, polyoxyethylene alkyl sulfates.
• Anionic surfactants such as ester salts, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester , Oxyethylene oxypropylene block copolymer and other nonionic surfactants are preferred.
• the Surfinol (registered trademark) series manufactured by Nisshin Chemical Industry Co., Ltd. which is an acetylene-based polyoxyethylene oxide surfactant, is also preferably used.
• amine oxide type amphoteric surfactants such as N, N-dimethyl-N-alkylamine oxide are also preferable.
• Japanese Patent Application Laid-Open No. 59-157,636, pp. (37) to (38), Research Disclosure No. Those listed as surfactants described in 308119 (1989) can also be used.
• a fluorine-based or silicone-based compound a fluorine-based or silicone-based compound, a chelating agent typified by ethylenediaminetetraacetic acid (EDTA), or the like can also be used as needed.
• EDTA ethylenediaminetetraacetic acid
• the phthalocyanine compound represented by the general formula (1) of the present invention is dispersed in an aqueous medium, colored fine particles containing the phthalocyanine compound represented by the general formula (1) and an oil-soluble polymer are dispersed in the aqueous medium.
• the phthalocyanine compound represented by the general formula (1) dissolved in a high boiling point organic solvent may be dispersed in an aqueous medium.
• a dispersant or a surfactant can be used.
• Dispersers include simple stirrer and impeller stirring methods, in-line stirring methods, mill methods (for example, colloid mills, ball mills, sand mills, attritors, roll mills, agitator mills, etc.), ultrasonic methods, and high-pressure emulsification and dispersion methods (high-pressure homogenizer).
• mill methods for example, colloid mills, ball mills, sand mills, attritors, roll mills, agitator mills, etc.
• ultrasonic methods for example, colloid mills, ball mills, sand mills, attritors, roll mills, agitator mills, etc.
• high-pressure homogenizer high-pressure homogenizer
• a gorin homogenizer a microfluidizer, DeBEE2000, etc.
• aqueous medium a mixture containing water as a main component and, if desired, a water-miscible organic solvent can be used.
• the water-mixable organic solvent include alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol), polyvalent.
• Alcohols eg, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol
• glycol derivatives eg, , Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene Glycoldiacetate, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol monophenyl ether), amine
• the ink for inkjet recording of the present invention may contain a compound (additive) represented by the following general formula (II).
• Ar 20 represents a benzene ring or a naphthalene ring.
• R 21 to R 28 independently represent a hydrogen atom or a substituent.
• R 21 and R 22 may be combined to form a ring.
• R 23 and R 24 may be combined to form a ring.
• R 25 and R 26 may be combined to form a ring.
• R 27 and R 28 may be combined to form a ring.
• R 29 represents a substituent.
• k represents an integer from 0 to 4.
• Ar 20 represents a naphthalene ring
• k represents an integer from 0 to 6. If R 29 there are a plurality, may be with or different plural R 29 are the same respectively. If R 29 there are a plurality, may form a ring with a plurality of R 29 is bonded.
• the compound represented by the general formula (II) has at least one hydrophilic group.
• the compound represented by the general formula (II) is preferably a colorless water-soluble planar compound having more than 10 delocalized ⁇ electrons in one molecule.
• the water-soluble compound represented by the general formula (II) may be a fluorescent compound, but a compound without fluorescence is preferable, and the wavelength ( ⁇ max) of the absorption peak on the longest wave side is more preferably 350 nm.
• the compound is more preferably 320 nm or less and has a molar extinction coefficient of 10,000 or less.
• the upper limit of the number of delocalized ⁇ electrons in one molecule of the compound represented by the general formula (II) is not particularly limited, but 80 or less is preferable, 50 or less is preferable, and 30 or less is particularly preferable.
• more than 10 ⁇ electrons may form one large delocalized system, but may form two or more delocalized systems.
• a compound having two or more aromatic rings in one molecule is preferable.
• the aromatic ring may be an aromatic hydrocarbon ring, an aromatic heterocycle containing a heteroatom, or may be fused to form one aromatic ring.
• aromatic ring examples include a benzene ring, a naphthalene ring, an anthracene ring, a pyridine ring, a pyrimidine ring, a pyrazine ring, a triazine ring and the like.
• the compound represented by the general formula (II) is preferably water-soluble, and is preferably a compound that dissolves at least 1 g or more in 100 g of water at 20 ° C. A compound that dissolves 5 g or more is more preferable, and a compound that dissolves 10 g or more is most preferable.
• R 21 to R 28 independently represent a hydrogen atom or a substituent.
• substituents include a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted hetero ring.
• R 21 to R 28 each independently represent a hydrogen atom or an alkyl group.
• the alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and most preferably an alkyl group having 1 to 6 carbon atoms. It is preferable that the alkyl group has the above-mentioned hydrophilic group as a substituent from the viewpoint of storage stability of the water-based ink.
• R 21 and R 22 , R 23 and R 24 , R 25 and R 26 , and R 27 and R 28 may be combined to form a ring, respectively.
• the ring is not particularly limited, but may be an aromatic ring or a non-aromatic ring, and a 5-membered ring or a 6-membered ring is preferable. Further, the ring may contain a hetero atom (for example, an oxygen atom, a nitrogen atom, a sulfur atom) in addition to the nitrogen atom to which R 21 to R 28 are bonded.
• R 29 represents a substituent, and the above-mentioned substituent is the same as that described as the above-mentioned substituent when R 21 to R 28 represent a substituent.
• R 29 preferably represents an ionic hydrophilic group or a substituted or unsubstituted alkyl group.
• the alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and most preferably an alkyl group having 1 to 6 carbon atoms. If R 29 there are a plurality, may be with or different plural R 29 are the same respectively. If R 29 there are a plurality, may form a ring with a plurality of R 29 is bonded.
• the ring is not particularly limited, but may be an aromatic ring or a non-aromatic ring, and a 5-membered ring or a 6-membered ring is preferable. Further, the ring may contain a hetero atom (for example, an oxygen atom, a nitrogen atom, a sulfur atom).
• At least one of R 21 to R 29 has a hydrophilic group.
• Hydrophilic groups are the I / O calculated values of ⁇ 0: organic value ⁇ and ⁇ I: inorganic value ⁇ and the hydrophobicity of the compound, which are outlined in the New Organic Conceptual Diagram-Basics and Applications- (Sankyo Publishing Co., Ltd.).
• LogP value (usually 1-octanol / molecular partition coefficient P in an aqueous system) or its calculated value ClogP value and acid dissociation constant of functional groups (pKa value), which are widely used in the fields of chemistry and pharmaceuticals as values of sex parameters. ) Can be easily selected as a substituent.
• hydrophilic group the “strongly hydrophilic group” and the “not very hydrophilic group” in the explanation of "hydrophilic group” in the 4th edition of the Chemical Dictionary (Kyoritsu Shuppan Co., Ltd.) are also preferable.
• the coloring composition (ink for inkjet recording) of the present invention is preferably used in a basic manner, a group having a high acid dissociation constant (pKa value) of a hydrophilic group and not having a strong hydrophilicity can also be applied.
• a group having a high acid dissociation constant (pKa value) of a hydrophilic group and not having a strong hydrophilicity include -NH 2 , -OH, and -CO 2 H (or alkali metal salts of carboxy groups).
• Further preferable hydrophilic groups include, in addition to the ionic hydrophilic group, a hydroxy group, an alkylcarbonylamino group, an arylcarbonylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, a quaternary ammonium group and the like.
• hydrophilic group an ionic hydrophilic group is preferable, a sulfo group (-SO 3 M) and a carboxy group (-CO 2 M) are more preferable, and a sulfo group (-SO 3 M) is most preferable.
• the ionic hydrophilic group includes a sulfo group (-SO 3 M), a carboxy group (-CO 2 M), a thiocarboxy group, a sulfino group (-SO 2 M), and a phosphono group (-PO (OT) (OM)).
• a sulfo group (-SO 3 M), a carboxy group (-CO 2 M), a thiocarboxy group, a sulfino group (-SO 2 M), and a phosphono group (-PO (OT) (OM)).
• quaternary ammonium group Dihydroxyphosphino group, phosphate group (-PO (OM) 2 ), quaternary ammonium group, acylsulfamoyl group (-SO 2 N - M + COT), sulfonylcarbamoyl group (-CON - M + SO
• the above M represents a hydrogen atom or a countercation.
• the above T is a monovalent substituent (-T).
• the ionic hydrophilic group is preferably an acidic group, and is at least one of a sulfo group (-SO 3 M), a carboxy group (-CO 2 M), and a phosphoric acid group (-PO (OM) 2). It is more preferably a sulfo group (-SO 3 M) or a carboxy group (-CO 2 M), and most preferably a sulfo group (-SO 3 M).
• M represents a hydrogen atom or a counter cation.
• M represents a counter cation, such as ammonium ion (NH 4 +), alkali metal ions (e.g., lithium ion, sodium ion, potassium ion, etc.), organic cations (e.g., tetramethylammonium ion, tetramethylguanidinium ion , Tetramethylphosphonium ion) and the like.
• a counter cation such as ammonium ion (NH 4 +), alkali metal ions (e.g., lithium ion, sodium ion, potassium ion, etc.), organic cations (e.g., tetramethylammonium ion, tetramethylguanidinium ion , Tetramethylphosphonium ion) and the like.
• M is preferably a hydrogen atom, an alkali metal cation or an ammonium ion, more preferably an alkali metal ion, further preferably a lithium ion, a sodium ion or a potassium ion, and is a lithium ion or a sodium ion. Is particularly preferable. Further, the counter cation may be only one kind (single salt) or two or more kinds (mixed salt).
• M may be a divalent counter cation.
• M be a divalent counter cation is, for example, two -SO 3 - can take such forms which also serves as one of the M counter cation of. From the viewpoint of water solubility, M is preferably a monovalent counter cation.
• the compound represented by the general formula (II) preferably has 1 to 10 hydrophilic groups in one molecule, and more preferably 2 to 8 hydrophilic groups.
• the compound represented by the general formula (II) preferably has 2 to 6 ionic hydrophilic groups in one molecule, and more preferably 2 to 4 ionic hydrophilic groups.
• At least one of R 21 to R 29 in the general formula (II) preferably has an ionic hydrophilic group, more preferably -SO 3 M, and 2 to 6 of R 21 to R 29. More preferably having a -SO 3 M, two to 4 R 21 ⁇ R 29 is particularly preferably has a -SO 3 M.
• Ar 20 represents a benzene ring or a naphthalene ring, and preferably represents a benzene ring.
• k represents an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0 or 1.
• Ar 20 represents a naphthalene ring
• k represents an integer of 0 to 6, preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and further preferably 0 or 1. preferable.
• the coloring composition and the inkjet recording ink of the present invention contain a compound represented by the general formula (II), the content of the compound represented by the general formula (II) is the coloring composition and the inkjet recording ink. It is preferably 0.1 to 1.0% by mass, more preferably 0.3 to 0.7% by mass, and 0.4 to 0.6% by mass based on the total mass of the above. Is more preferable.
• the compound represented by the general formula (II) can be synthesized by a known method (for example, the method described in Japanese Patent No. 4686151).
• the type of the compound represented by the general formula (II) may be one kind or two or more kinds. good.
• the coloring composition and the ink for inkjet recording of the present invention may be used in combination with another dye in combination with the phthalocyanine compound represented by the general formula (1).
• the total content of the dyes is in the above range.
• the ink for inkjet recording of the present invention preferably has a viscosity of 30 mPa ⁇ s or less.
• the surface tension is preferably 25 mN / m or more and 70 mN / m or less. Viscosity and surface tension can be determined by various additives such as viscosity modifiers, surface tension modifiers, specific resistance modifiers, film modifiers, UV absorbers, antioxidants, anti-fading agents, fungicides, rust inhibitors. , Dispersants and surfactants can be added.
• the inkjet recording ink of the present invention can be used not only for forming a single color image but also for forming a full color image.
• Magenta tones, cyan tones, and yellow tones can be used to form full-color images, and black tones may be further used to adjust the tones.
• the inkjet recording method of the present invention supplies energy to the above-mentioned inkjet recording ink to provide known image receiving materials, that is, plain paper, resin-coated paper, for example, JP-A-8-169172A, JP-A-8-27693, the same. 2-276670, 7-276789, 9-323475, 62-238783, 10-153989, 10-217473, 10-235995. , 10-337947, 10-217597, 10-337947, etc. Form images on inkjet paper, film, electrophotographic paper, cloth, glass, metal, ceramics, etc. To do.
• a polymer fine particle dispersion (also referred to as polymer latex) may be used in combination for the purpose of imparting glossiness and water resistance and improving weather resistance.
• the time to apply the polymer latex to the image receiving material may be before, after, or at the same time as the colorant is applied, and therefore the place of addition may be in the image receiving paper. It may be used in ink or as a liquid substance of polymer latex alone.
• the recording paper and recording film used for performing inkjet printing using the ink of the present invention will be described below.
• the support in the recording paper and the recording film is made of chemical pulp, mechanical pulp, waste paper pulp, etc., and if necessary, additives such as conventionally known pigments, binders, sizing agents, fixing agents, cation agents, and paper strength enhancers. Can be used, such as those manufactured by various devices such as a long-net paper machine and a circular-net paper machine.
• synthetic paper or a plastic film sheet may be used, and the thickness of the support is preferably 10 to 250 ⁇ m and the basis weight is preferably 10 to 250 g / m 2.
• the support may be provided with an ink receiving layer and a back coat layer as they are, or may be provided with a size press or an anchor coat layer with starch, polyvinyl alcohol or the like, and then an ink receiving layer and a back coat layer may be provided. Further, the support may be flattened by a calendar device such as a machine calendar, a TG calendar, or a soft calendar.
• a calendar device such as a machine calendar, a TG calendar, or a soft calendar.
• paper and plastic films in which both sides are laminated with polyolefin for example, polyethylene, polystyrene, polyethylene terephthalate, polybutene and copolymers thereof
• a white pigment for example, titanium oxide, zinc oxide
• a coloring dye for example, cobalt blue, ultramarine blue, neodymium oxide
• the obtained compound (mixture) high performance liquid chromatography and MALDI-MS (Matrix Assisted Laser Desorption / Ionization-Mass Spectrometry) was analyzed using a nitro group / -SO 2 -Z 1 group of the phthalocyanine compound in one molecule Is a mixture containing the above compounds (a1), (a2), (a3), and (a4) in which the number of substitutions is 0/4, 1/3, 2/2, and 3/1, and the whole is averaged. It was confirmed that it was Exemplified Compound 1-1.
• Comparative compounds 1, 2 and 3 were synthesized using the method described in Japanese Patent No. 39949385.
• Comparative Compound 4 was similarly synthesized by changing 3-nitrophthalonitrile used in Synthesis Example 1 to 4-nitrophthalonitrile.
• Phthalocyanine compound (Example compound 1-1) 0.48 g Glycerin 1.48g Triethylene glycol monobutyl ether 1.45g 2-Pyrrolidone 0.34 g Triethylene glycol 0.29g Surfinol 465 0.14g
• the above-mentioned Surfinol 465 is a surfactant, and is Surfinol (registered trademark) 465 manufactured by Nisshin Chemical Industry Co., Ltd.
• ink liquids B to E and 101 to 10 were prepared in the same manner as in the preparation of ink liquid A, except that the phthalocyanine compound (exemplified compound 1-1) was changed as shown in Table 1 below. did.
• Ink liquid F composition Phthalocyanine compound (Example compound 1-1) 0.48 g Glycerin 1.48g Triethylene glycol monobutyl ether 1.45g 2-Pyrrolidone 0.34 g Triethylene glycol 0.29g Surfinol 465 0.14g Compound X 0.05g
• ⁇ Robustness against ozone gas> A 5 kV AC voltage is applied while passing dry air through the double glass tube of the Siemens type ozonizer, and the ozone gas concentration is 10.0 ⁇ 0.5 ppm (parts per image), room temperature (20 ° C), and dark place.
• the photo-glossy paper on which the image is formed is left for 60 hours, and the image density after being left under ozone gas is measured by a reflection densitometer (trade name i1 PUBLISH PRO) equipped with a status A filter (Red) as standard equipment. 2.
• the dye residue ratio was calculated from the initial image concentration Ci and the image concentration Cf after being left under ozone gas.
• the initial image density Ci is measured using an optical reflection density of about 1, and the dye residual rate at 20 hours (ozone fastness 1) and 60 hours (ozone fastness 2) over time is evaluated. , Robustness against ozone gas was evaluated.
• the ozone gas concentration in the box was set using an ozone gas monitor manufactured by APPLICS (model: OZG-EM-01).
• the dye residual ratio was calculated from the following formula, and the robustness to ozone gas was evaluated according to the following criteria.
• Dye residual rate (%) (Cf / Ci) x 100
• ⁇ Ozone fastness 2> When the dye residual rate is 85% or more in 60 hours B: When the dye residual rate is 75% or more and less than 85% in 60 hours C: When the dye residual rate is less than 75% in 60 hours
• the OD (Optical Density) value is 0.7 to 0.7 using the inkjet recording inks of the respective Examples (ink solutions A to F) and Comparative Examples (ink solutions 101 to 104).
• An image pattern in which the density was changed stepwise so as to be 1.8 was printed.
• a * and b * were measured using an image having an OD of 1 ⁇ 0.2. From the values of a * and b * of the image, the value of the hue angle H ° was calculated based on the following formula.
• H ° is 225 ° or more and less than 235 °
• B H ° is 0 ° or more and less than 225 °, or 235 ° or more and less than 360 °
• a coloring composition having excellent fastness to ozone gas and excellent storage stability when used as a conch ink, an inkjet recording ink containing the coloring composition, and an inkjet recording method using the inkjet recording ink.
• a phthalocyanine compound that can be used as a dye in the above coloring composition can be provided.

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• Inks, Pencil-Leads, Or Crayons (AREA)
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