WO2002088256A1 - Colorant soluble dans l'eau et resistant a l'oxydation forme d'un complexe cuivre/compose de phtalocyanine, composition de colorant contenant ce complexe et fluide de marquage - Google Patents

Colorant soluble dans l'eau et resistant a l'oxydation forme d'un complexe cuivre/compose de phtalocyanine, composition de colorant contenant ce complexe et fluide de marquage Download PDF

Info

Publication number
WO2002088256A1
WO2002088256A1 PCT/JP2002/004331 JP0204331W WO02088256A1 WO 2002088256 A1 WO2002088256 A1 WO 2002088256A1 JP 0204331 W JP0204331 W JP 0204331W WO 02088256 A1 WO02088256 A1 WO 02088256A1
Authority
WO
WIPO (PCT)
Prior art keywords
dye
water
rings
ring
general formula
Prior art date
Application number
PCT/JP2002/004331
Other languages
English (en)
Japanese (ja)
Inventor
Kaoru Takahashi
Original Assignee
Daiwa Dyestuff Mfg. Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Daiwa Dyestuff Mfg. Co., Ltd. filed Critical Daiwa Dyestuff Mfg. Co., Ltd.
Publication of WO2002088256A1 publication Critical patent/WO2002088256A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/328—Inkjet printing inks characterised by colouring agents characterised by dyes
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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

Definitions

  • the present invention relates to a water-soluble copper phthalocyanine compound complex dye, and a recording liquid using the same, particularly, a recording liquid used in an ink jet recording method.
  • Ink jet recording is a printing method in which droplets of ink composition are ejected and deposited on a recording medium such as paper to perform printing.
  • the color reproduction of the obtained image is roughly performed using three ink compositions of cyan, magenta, and yellow.
  • phthalocyanine dyes are widely used at present because of their high chromaticity, light fastness and heat resistance, and in particular, Direct Blue 19 9 is a cyan ink for ink jet printing. Is widely used as a dye. It has excellent light resistance and heat resistance, but it is resistant to oxidants such as atmospheric ozone, nitrogen oxides (NOx), sodium hypochlorite in aqueous solution, and chlorine. It has the disadvantage of fading in a short time.
  • oxidants such as atmospheric ozone, nitrogen oxides (NOx), sodium hypochlorite in aqueous solution, and chlorine.
  • the ink composition liquid is improved as an ink composition liquid, for example, the ink composition liquid contains an antioxidant, a radical reaction inhibitor or the like, or a film is formed on the surface of the ink jetted on paper. Tree with the ability PC leak 2/04331
  • Discharges a protective solution containing grease Discharges a protective solution containing grease.
  • An example of improving the resistance by these protective liquids is described in JP-A-2000-225695.
  • the improvement of the recording medium improves the resistance of the recorded matter to oxidizing gases such as ozone in the air.
  • oxidizing gases such as ozone in the air.
  • JP-A-8-164664, JP-A-9-254526, and the like It is described in the official gazette.
  • JP-A-2000-303009 discloses that phthalocyaninesulfonic acid synthesized from 4-sulfophthalic acid is phthalocyaninated sulfonic acid sulfonated after synthesis of a lidar cyanine skeleton. It is described that N and sulfonamide are more resistant to nitric oxide.
  • the present invention has been made to solve the above-mentioned problems, and an object thereof is to use an oxidizing substance such as ozone in the air or an oxidizing substance such as chlorine in an aqueous solution or an oxidizing substance such as hypochlorite. It is an object of the present invention to provide a water-soluble dye, a dye composition and a recording liquid, particularly a recording liquid for ink jets, having higher resistance than the dye and having high safety.
  • FIG. 1 shows the time change of absorbance measured for the dye solution containing the dye obtained in Examples 1 to 5 and the dye solution containing the comparative dye in the presence of sodium hypochlorite It is a graph. Disclosure of the invention
  • oxidizing compounds can be obtained by using a specific phthalocyanine compound complex water-soluble dye in the recording liquid, and further by adding a specific highly safe organic compound. It has been found that a highly safe recording liquid having high resistance to the above can be obtained, and the present invention has been made based on this finding.
  • the object of the present invention is achieved by the following (1) to (14).
  • a water-soluble dye comprising a compound represented by the following general formula (1).
  • one or two of the four rings A1 to A4 are a pyrimido ring, and the remaining is a methyl benzene ring.
  • Water-soluble dyes as described.
  • one or two of the four rings A1 to A4 are pyridine rings, and the remaining rings are a methylbenzene ring and a benzene ring (1)
  • the water-soluble dye according to Item is a methylbenzene ring and a benzene ring
  • n is 1 or more, and one S 2 2 NHR is-S 0 2 NH 2.
  • S 2 2 NHR is-S 0 2 NH 2.
  • n is 1 or more
  • —S 0 2 NHR is a amidosalicylic acid, serine, threonine, hydroxyphenylglycine or sulfonamide residue of cystine Is characterized by PC leak 31
  • (9) It is selected from the group consisting of the water-soluble dye or dye according to any one of items (1) to (8), 1 9 9, 1 8 6 and 6 8 It is characterized in that it contains at least one additive and at least one additive selected from the group consisting of serine, threonine, hydroxyglycinylglycine and sodium aminosalicylic acid.
  • Dye composition It is selected from the group consisting of the water-soluble dye or dye according to any one of items (1) to (8), 1 9 9, 1 8 6 and 6 8 It is characterized in that it contains at least one additive and at least one additive selected from the group consisting of serine, threonine, hydroxyglycinylglycine and sodium aminosalicylic acid.
  • a dye composition comprising: at least one selected from the group consisting of 9.
  • a recording liquid comprising one or more of the water-soluble dye or the dye composition according to any one of (1) to (12).
  • a recording liquid for ink jet comprising at least one water-soluble dye or dye composition according to any one of (1) to (12).
  • the water-soluble dye comprising the compound represented by the general formula (1) of the present invention will be described in detail.
  • the sum of the pyridine ring and / or the aromatic benzene ring in Al to A4 is preferably 1 to 2 and the pyridine ring is preferably 1 to More preferably, it is in the range of two. Furthermore, the configuration of A1 to A4 is particularly preferable in the case of 3 to 2 alkyl benzene rings or 1 to 2 pyridine rings.
  • Preferred examples of the alkylbenzene ring include methylbenzene, ethylbenzene, propylbenzene, isopropylbenzene and the like, with methylbenzene being particularly preferable o
  • a methylbenzene ring is particularly preferable as the alkyl benzene ring.
  • the dye of the present invention has at least one pyridine ring, oxidation resistance is increased, and there is almost no change in color due to pH fluctuation, which is preferable. For example, it is possible to prevent the color from changing to green under acid as in the case of direct blue 1 9 9.
  • the monovalent alkali metal represented by D is not particularly limited, and includes sodium, lithium, potassium and the like, with sodium and lithium being preferred.
  • Examples of the organic ammonium represented by D include, but are not limited to, ethanol amine, diethanol amine, triethanol amine, N, N-dimethyl ethanol amine and the like, with preference given to ethanol amine, It is a Jettano Rumin.
  • m is 2 to 3, and when m is 2 or more, it is preferable that one S0 3 D be substituted with a different ring among the four rings of A 1 to A 4.
  • a sulfonamide structure for example, sulfonamides such as amidosalicylic acid, serine, threonine, hydroxyphenylglycine, cystine and the like can be mentioned, and preferably, aminosalicylic acid, serine, threonine, More preferred are aminosalicylic acid and threonine, and particularly preferred is a sulfonamide of aminosalicylic acid.
  • SO 2 NHR it is preferable to use a single SO 2 NH 2 s to raise the chromaticity in a small amount, and to further increase the resistance to oxidizing substances in aqueous solution, aminosalicylic acid, Se Li down, preparative Reonin arsenide Dorokishifue two caprylyl thin, rather then preferred that residues sulfonamide de cystine etc., when a plurality chromatic an S0 2 NHR may be these groups sac Chino different combinations .
  • Preferred n is 1 to 3, and more preferably n is 1 to 2.
  • n is 2 or more, it is preferable that one S0 2 NHR is substituted by a different ring among four rings of A 1 to A 4.
  • —S0 2 NHR is a sulfonamide residue of amaminosalicylic acid, serine, threonine, hydroxyphenylglycine or cystine It is preferably a group, more preferably a sulfonamide residue of aminosalicylic acid or threonine.
  • the compounds represented by the general formula (1) of the present invention can be used as the raw materials in the form of phthalic anhydride, alkylphthalic anhydride (eg, 4-methylphthalic anhydride), quinolinic acid or phthalic anhydride.
  • Skeletal synthesis can be performed according to a known Wyler method using a high boiling point solvent such as an acid (for example, 4-chloro-anhydride), urea, copper chloride, a molybdenum catalyst, tri-chloro benzene, alkyl benzene and the like.
  • the use ratio of hydrofluoric anhydride and quinolinic acid, or of hydrofluoric anhydride and hydrofluoric anhydride anhydride can be based on known conditions, and is not particularly limited. Although it is not, for example, it is preferable that the molar ratio is 4: 0 to 2: 2.
  • the use ratio of alkyl phthalic anhydride and quinolinic acid, or alkyl phthalic anhydride and open mouth phthalic anhydride can be based on known conditions and is particularly limited. Although not preferred, for example, the molar ratio is preferably 4: 0 to 2: 2.
  • alkyl hydrofluoric anhydride, hydrofluoric anhydride and quinolinic acid, or alkyl hydrofluoric anhydride, hydrofluoric anhydride and crocodile hydrofluoric acid is particularly limited.
  • the molar ratio is 3: 0: 1 to 1: 1: 2.
  • the compound thus obtained is chlorosulfonated in chlorosulfonic acid and then obtained as a sulfonic acid compound, it can be obtained by hydrolysis with an aqueous solution of Na OH or the like.
  • an ammonia component, ammonia, or an amine an amine capable of forming a complex with a copper ion after formation of a sulfon amide, can be added to the chlorosulfonate);
  • it is reacted with 1 to 2 molar ratio, preferably 2 molar ratio).
  • the reaction is carried out using water or acetone as a solvent, the reaction pH is preferably 8 to 10, and the temperature is usually 0 to 60 ° C, preferably 20 to 40 ° C.
  • the compound represented by the general formula (1) of the present invention is a sulfonated non-phthalic acid, a sulfonated hydrofluoric acid or a sulfonated alkyl phthalic acid, a sulfonated chlorophthalic acid, a urea, a copper chloride, It is also possible to synthesize using a molybdenum catalyst as a raw material and using trichlorobenzene and alkylbenzene as a solvent according to the well-known Wyler method.
  • the water-soluble dye comprising the compound represented by the general formula (1) of the present invention can be prepared from the reaction mixture by a conventional treatment method, for example, by salting-out filtration or acid precipitation filtration, if necessary desalting with a filtration membrane. It can be separated by microfiltration.
  • the water-soluble dye comprising the compound represented by the general formula (1) of the present invention can be used to record characters and figures on natural fiber materials, dyeing of synthetic fiber materials, printing, especially various recording materials. .
  • the dye represented by the general formula (1) of the present invention is suitable as a recording solution, in particular, a recording solution for ink jet printing.
  • the dye comprising the compound represented by the general formula (1) of the present invention is particularly suitable for ozone in the air and in aqueous solution, as compared to CI Direct Blue 199, which is widely used for cyan ink of inkjet method. It is highly resistant to oxidizing substances such as hypochlorous acid sodium.
  • the dye composition containing the dye consisting of the compound represented by General formula (1) of this invention is demonstrated in detail. .
  • the dye composition of the present invention is preferably 0.5 to 15% by mass (calculated in the dry state), more preferably 1 to 4% by mass, of the general formula (1) (preferably one or more kinds) It contains a water-soluble dye consisting of the compound represented.
  • the dye composition is a dye solution, it is preferable to further contain 0 to 99% by mass of water and 0.5 to 99.5% by mass of a solvent and / or a wetting agent.
  • One particularly preferable composition of the dye solution is a water-soluble dye comprising a compound (preferably one or more kinds) represented by the general formula (1) of 0.5 to 15% by mass (calculated on a dry basis). And 40 to 85% by weight of water and 10 to 50% by weight of solvents and / or wetting agents.
  • a water-soluble dye comprising a compound (preferably one or more kinds) represented by the general formula (1) of 0.5 to 15% by mass (calculated on a dry basis) And 0 to 20% by weight of water and 70 to 99.5% by weight of solvents and / or wetting agents.
  • the composition When a compound capable of forming a complex with copper ion is added to a dye composition containing a water-soluble dye comprising a compound represented by the general formula (1) of the present invention, the composition is particularly effective when used as an aqueous solution. Antioxidant action is further improved.
  • usable and safety-recommended additives there may be mentioned various amino acids, salicylic acid, EDTA and the like, and amino acids and the like are used in food and medicine and are highly safe. More preferably, it is cellulose, threonine, hydroxyphenylglycine or aminosalicylic acid sodium.
  • the amount of the additive used is preferably 1 to 20% by mass, more preferably 3 to 10% by mass, particularly preferably 6 to 10% by mass with respect to the water-soluble dye.
  • the dye composition of the present invention may be a phthalocyanine dye other than the dye of the present invention other than the dye consisting of the compound represented by the general formula (1) of the present invention, for example, dye blue 86, 87, 199 or Triphenylmethane dyes, for example, Acid Bull 9 may be contained as required. In that case, it is preferable because the oxidation resistance is further improved as compared with the use of a phthalocyanine dye other than the present invention alone.
  • inorganic salts such as sodium chloride and sodium sulfate can be preferably contained.
  • amines such as ethanolamine, ketoanamine, triethanolamine, N, N-dimethylethanolamine, diisopropylamine are used to increase P H. It is also good. These amines can generally be present in the dye solution in the range of 0 to 10% by mass, preferably 0.5 to 5% mass.
  • the pH of the dye solution is preferably 4 to 11, more preferably 6 to 10.
  • the dye composition or dye liquid of the present invention may be added with various additives conventionally used in order to further improve properties such as storage stability, dissolution stability of water-soluble dye, weatherability and the like. Good.
  • various additives conventionally used in order to further improve properties such as storage stability, dissolution stability of water-soluble dye, weatherability and the like.
  • viscosity modifiers such as celluloses, water soluble resins, etc., cations, anions, and various nonionic surfactants.
  • the recording liquid of the present invention contains the water-soluble dye and / or the dye composition, but the composition, the dye which may be used in combination, and the pH of the recording liquid are selected from the same range as in the case of the dye liquid.
  • the preferred range can also be selected from the same range as described above.
  • Water which can be used in the recording liquid of the present invention is, in particular, distilled water, ion exchange Water or demineralized water is preferred.
  • the solvents and wetting agents that can be used in the recording liquid may be single solvents and their wetting agents or mixtures.
  • Preferred solvents for use are water-soluble organic solvents.
  • Solvents which can be used are, for example, monohydric or polyhydric alcohols and ethers, esters thereof, such as alphorols, in particular those having 1 to 4 carbon atoms, such as methanol, ethanol, propanol, isopropano Mono-, di- and tri-butanol, dihydric and trihydric alcohols, alcohols having 2 to 6 carbon atoms, such as ethylene glycol, propylene glycol, 1,3-propanediol, 1 , 4-butyldiol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 2, 6-hexanethiol, glycerol, glycol glycol, and dipropylene glycol, polyarykilene glycol Alcohols such as triethylene glycol, polyethylene glycol, tripropylene glycol and polypropylene Pyrene glycol; lower alkyl ethers of polyhydric alcohols, such as ethylene glycol monomethyl or ethy
  • diethylene glycol, glycerol, ethylene glycol monomethyl ether, and more preferably diethylene glycol and glycerol are preferred.
  • recording characteristics signal response, droplet formation stability, ejection stability
  • storage stability dissolution stability of water-soluble dye
  • fixing stability to recording member recording image
  • additives conventionally used to further improve the properties such as weather resistance
  • viscosity modifiers such as celluloses and water-soluble resins
  • surfactants such as cations, anions and nonionics.
  • the dye comprising the compound represented by the general formula (1) according to the present invention, and the dye composition and recording liquid using the same have excellent resistance to oxidizing substances, but they have the following 1) to 3) It is thought that it is due to one or a combination of factors.
  • a pyridine ring is introduced into a part of the lidar cyanine skeleton as a skeleton having resistance to an oxidizing substance.
  • one S0 2 NHR is introduced into the phthalocyanine side chain as a substituent which forms a complex with the copper ion, and free copper is produced when the phthalocyanine skeleton is decomposed. Poisons oxidation catalysis.
  • the dye of the present invention exhibits the excellent effects of being highly resistant to oxidizing substances in air or aqueous solution, and highly safe.
  • the dye composition of the present invention has the above-mentioned properties, and can further improve the oxidation resistance by adding an appropriate compound without deteriorating the safety.
  • a recording liquid containing these dyes and Z or a dye composition has the above-mentioned properties, and an image reproduced by using this recording liquid exhibits an excellent effect that fading is extremely little.
  • the recording liquid of the present invention is particularly suitable as a recording liquid for ink jet recording.
  • the resulting precipitate was dispersed in 300 ml of 4 to 5% hydrochloric acid at 60 to 65 ° C. for 30 minutes and stirred, and then collected by filtration.
  • the precipitate is dispersed and stirred in 300 ml of a 5% aqueous solution of NaOH for 30 minutes, and filtered, and the obtained precipitate is treated with 300 ml of deionized water. Washing was performed to obtain a copper-phthalocyanine compound complex (yield 29.8 g).
  • the mixture is cooled to room temperature, gradually discharged onto 500 g of ice, and collected by filtration. It was washed with 200 ml of water.
  • the precipitate obtained was dispersed and stirred in 180 ml of ion-exchanged water, and 30 ml of a 20% aqueous solution of NaOH was added to prepare a total liquid volume of 300 ml and stirred at 60 to 65 ° C. for 2 hours.
  • the pH of the reaction solution is adjusted to 7.0 to 7.5, 300 ml of ethanol is added, and the deposited precipitate is collected by filtration, and 80% ethanol is added until the filtrate of the precipitate does not precipitate white with an aqueous solution of silver chloride. The precipitate was washed.
  • the water-soluble dye can be obtained by membrane filtration or the like to obtain a dye of a quality which can be used in the ink jet method.
  • 35 g of copper phthalocyanin was gradually added to 210 g of chlorosulfonic acid and stirred at 125 to 135 ° C. for 4 hours.
  • 45 ml of thionyl chloride was gradually added dropwise and stirred at 80 to 85 ° C for 4 hours.
  • the mixture was gradually discharged onto 1 kg of ice containing 150 ml of saturated brine, and the precipitate was collected by filtration and washed with 500 ml of ice-cold water.
  • the obtained cake-like precipitate is dispersed and stirred in 300 ml of ion-exchanged water and 200 g of ice, and the pH is adjusted to 6.5 to 7.0 with a 25% aqueous solution of NaOH.
  • An aqueous solution of salicylic acid (14.0 g of 5-aminosalicylic acid was dispersed and stirred in 60 ml of ion-exchanged water, and 3.7 g of NaOH was added and dissolved at room temperature) was gradually added dropwise.
  • the mixture is stirred at 0 to 10 ° C. for 1 hour, at 20 to 30 ° C. for 3 hours, at 30 to 40 ° C. for 2 hours while maintaining pH 8.5 to 1: 100, and pH 9.8. 7 to 8 0.
  • the mixture was stirred for 1 hour.
  • the reaction solution is cooled to room temperature, 100 g of concentrated hydrochloric acid is added, and the mixture is stirred for 30 minutes.
  • the precipitate is collected by filtration and washed with 200 ml of ion exchanged water.
  • the obtained acid precipitate was dispersed in 800 ml of ion-exchanged water while stirring and a 25% aqueous solution of NaOH was added dropwise to adjust the pH to 7.0 to 6.5 while heating and dissolving at 70 to 80 ° C. (total liquid volume 900 ml).
  • the solution was allowed to cool to room temperature, 100 g of concentrated hydrochloric acid was added, the mixture was stirred for 30 minutes, and the mixture was collected by filtration, and the acid precipitate was washed with 300 ml of deionized water.
  • the obtained acid precipitate was dispersed and stirred in 150 ml of ion-exchanged ice, and a 25% aqueous solution of NaOH was added dropwise to adjust the pH to 7.0 to 6.5 while heating to dissolve at 70 to 80 ° C. and then returned. 900 ml of ethanol was added to this solution and stirred for 30 minutes, the precipitate was collected by filtration, and washed with 300 ml of 80% ethanol.
  • the desalted product suitable for the ink preparation of the above water-soluble dye by ink-jetting can also be obtained by membrane filtration.
  • composition obtained was added to 800 ml of 3% hydrochloric acid, dispersed and stirred at 80 to 90 ° C. for 1 hour, and filtered.
  • the obtained precipitate was dispersed and stirred in 300 ml of ion-exchanged water and 200 g of ice, and after adjusting the pH to 6.5 to 7.0 with a 25% aqueous NaOH solution, 5.5 g of concentrated aqueous ammonia was gradually added dropwise.
  • the reaction solution was returned to room temperature, 100 g of concentrated hydrochloric acid was added, and after 30 minutes of stirring, the precipitate was collected by filtration and washed with 200 ml of ion exchanged water.
  • the resulting acid precipitate was dispersed in 800 ml of ion-exchanged water and stirred, and a 25% aqueous solution of NaOH was added dropwise to adjust the pH to 7.0 to 6.5 while heating and dissolving at 70 to 80 ° C. (Total liquid volume 900 ml)
  • the solution was allowed to cool to room temperature, 100 g of concentrated hydrochloric acid was added, and the mixture was stirred for 30 minutes, then collected by filtration and washed with 300 ml of ice-exchanged ice.
  • the obtained acid precipitate was dispersed and stirred in 150 ml of deionized water, and 25% aqueous NaOH was added dropwise to adjust the pH to 7.0 to 6.5 while heating and dissolving to 70 to 80 ° C., and then returned to room temperature.
  • 900 ml of ethanol was added to the solution and stirred for 30 minutes. The precipitate was collected by filtration and washed with 300 ml of 80% ethanol.
  • the four rings of A 1 to A 4 have about 3 benzene rings and about 1 open benzene ring, and —S 0 3 D—
  • the resulting precipitate was dispersed and stirred in 250 ml of 3 to 4% hydrochloric acid at 80 to 85 ° C. for 30 minutes, and then collected by filtration.
  • the precipitate was dispersed and stirred in 250 ml of 3% aqueous NaOH solution for 30 minutes, and filtered, and the obtained precipitate was washed with 300 ml of deionized water.
  • the precipitate is dispersed and stirred in 250 ml of 3 to 4% hydrochloric acid at 80 to 85 ° C. for 30 minutes and then filtered, and the obtained precipitate is washed with 300 ml of ion-exchanged water, and copper phthalocyanine and Russianin compound complex I got (Yield 26.4g)
  • the precipitate obtained was dispersed and stirred in 300 ml of ion exchanged water, and stirred for 2 hours while adjusting the pH to 9 to 11 at 70 to 80 ° C. using 20% NaOH.
  • the volume of the reaction solution was adjusted to 800 ml, 100 g of concentrated hydrochloric acid was added at room temperature, acid precipitation was performed, and filtration was performed, and the acid precipitate was washed with 400 ml of ion exchanged water.
  • the obtained acid precipitate is dispersed in 300 ml of ion-exchanged water, adjusted to pH 7.0 to 7.5 using a 20% aqueous NaOH solution at 70 to 80 ° C., and filtered.
  • the water-soluble dye can be a membrane filtration or the like to obtain a dye of a quality which can be used in the ink jet method.
  • the solvent for decantation was removed at ⁇ 80 ° C, 150 ml of 70% ethanol was added to the residue, the mixture was stirred for 30 minutes, and after standing, the supernatant was removed by decantation. After 70% ethanol was added to the residue again, the mixture was stirred at 70 to 80 ° C for 30 minutes.
  • the resulting precipitate was dispersed and stirred in 250 ml of 3 to 4% hydrochloric acid at 80 to 85 ° C. for 30 minutes, and then collected by filtration.
  • the precipitate was dispersed and stirred in 250 ml of 3% aqueous NaOH solution for 30 minutes, and filtered, and the obtained precipitate was washed with 300 ml of deionized water.
  • the precipitate was again dispersed and stirred in 250 ml of 3 to 4% hydrochloric acid at 80 to 85 ° C. for 30 minutes, followed by filtration, and the obtained precipitate was washed with 300 ml of ion-exchanged water to obtain a copper phthalocyanine compound complex. . (Yield 25.7g)
  • the precipitate obtained was dispersed and stirred in 300 ml of ion exchanged water, and stirred for 2 hours while adjusting the pH to 9 to 11 at 70 to 80 ° C. using 20% NaOH.
  • the volume of the reaction solution was adjusted to 800 ml, 100 g of concentrated hydrochloric acid was added at room temperature, acid precipitation was carried out, filtration was carried out, and the acid precipitate was washed with 400 ml of ion exchanged water.
  • the obtained acid precipitate is dispersed in 300 ml of ion-exchanged water, adjusted to pH 7.0 to 7.5 using a 20% aqueous NaOH solution at 70 to 80 ° C., and filtered to obtain 800 ml of mother liquor and 100 g of concentrated hydrochloric acid at room temperature. Acid was added. The precipitate was filtered and washed with 400 ml of ion-exchanged water.
  • the obtained reacidification product is dispersed in 300 ml of ion-exchanged water, adjusted to pH 7.0-7.5 using a 20% aqueous solution of NaOH at 70-80 ° C., concentrated under reduced pressure to a liquid volume of 250 ml, and ethanol Add 750 ml and filter off the deposited precipitate until the filtrate of the precipitate does not white precipitate with aqueous silver chloride solution The precipitate was washed with 80% ethanol.
  • the four rings A1 to A4 have about 1.33 methylbenzene rings, about 1.35 5 benzene rings, and about 4 pyridine rings.
  • the water-soluble dye can be obtained by membrane filtration or the like to obtain a dye of a quality which can be used in the ink jet method.
  • the oxidation resistance to the oxidizing substance when the dye of the present invention or the conventional dye was used as a dye solution was tested as follows. Hypochlorous acid sodium resistance test
  • a dye solution containing the dye of the present invention or a dye for comparison is The following test was made on the fading when used as a recording solution for printing
  • aqueous solution was prepared such that the dye concentration was 3% for each of the direct blue 199 and the dyes obtained in the above examples.
  • Each recording solution is a piece of paper for inkjet paper (manufactured by Kao Corp., trade name: KJHA 4 0 0 0, 5 cm long, 10 cm wide) with a brush and the size of 2 cm by 1.5 cm After being evenly coated with the above, it was dried to obtain a sample sheet.
  • a piece of sample paper is suspended for 8 hours in a 2-liter closed plug vessel (500 cm above the liquid surface) containing 500 ml of sodium hypochlorite (effective chlorine 12 to 14%), and the color change is Was visually evaluated. Evaluation criteria were as follows.
  • the sample paper pieces were put in a container having an ozone concentration of 500 ppm for 1 hour, taken out, and then allowed to stand at room temperature for 24 hours to evaluate the color change visually. Evaluation criteria were as follows.
  • the dyes of the present invention are suitable for printing applications since they have high resistance to oxidizing substances in air or aqueous solution and high safety.
  • the dye composition of the present invention has the above-mentioned properties, and can further improve the oxidation resistance without deteriorating the safety by adding an appropriate compound, so it is suitable for printing applications and the like. It is
  • the recording liquid of the present invention containing the dye and / or the dye composition has the above-mentioned properties, and the image reproduced using this recording liquid is extremely less discolored, so the recording liquid of the present invention is Particularly, it is suitable as a recording liquid for ink jet recording. While the present invention has been described in conjunction with embodiments thereof, it is not intended to limit our invention in any detail of the description unless otherwise specified, and the spirit of the invention as set forth in the appended claims. I think that it should be interpreted broadly without contradicting the scope.

Abstract

La présente invention concerne un colorant soluble dans l'eau qui renferme un composé représenté par la formule (I) dans laquelle au moins un des quatre anneaux (A1) à (A4) représente un anneau alkylbenzène ou un anneau benzène, ou bien au moins deux de ces anneaux représentent respectivement un anneau alkylbenzène et un anneau benzène, les anneaux restants représentant chacun un anneau pyridine ou un anneau chlorobenzène; -SO3D et SO2NHR représentant des substituants présents sur (A1), (A2), (A3) ou (A4); D représente un métal alcalin monovalent, ammonium ou un ammonium organique; m est compris entre 1 et 4; -SO2NHR représente SO2NH2 ou un reste sulfonamide capable de former un complexe avec un ion cuivre; et n est compris entre 0 et 3, à condition que lorsque n est égal à 0, tous les quatre anneaux (A1) à (A4) ne représentent pas un anneau benzène. Formule (I)
PCT/JP2002/004331 2001-04-27 2002-04-30 Colorant soluble dans l'eau et resistant a l'oxydation forme d'un complexe cuivre/compose de phtalocyanine, composition de colorant contenant ce complexe et fluide de marquage WO2002088256A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2001133308 2001-04-27
JP2001-133308 2001-04-27

Publications (1)

Publication Number Publication Date
WO2002088256A1 true WO2002088256A1 (fr) 2002-11-07

Family

ID=18981185

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2002/004331 WO2002088256A1 (fr) 2001-04-27 2002-04-30 Colorant soluble dans l'eau et resistant a l'oxydation forme d'un complexe cuivre/compose de phtalocyanine, composition de colorant contenant ce complexe et fluide de marquage

Country Status (1)

Country Link
WO (1) WO2002088256A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003062323A1 (fr) * 2002-01-22 2003-07-31 Fuji Photo Film Co., Ltd. Encre contenant un compose de phtalocyanine soluble dans l'eau pour impression a jet d'encre, procede d'impression a jet d'encre et procede reduisant la decoloration due a l'ozone dans une image coloree
EP1462492A1 (fr) * 2003-03-27 2004-09-29 Fuji Photo Film Co., Ltd. Encre et assortiment d'encre
JP2005179469A (ja) * 2003-12-18 2005-07-07 Fuji Photo Film Co Ltd フタロシアニン化合物、インク、インクジェット記録方法、および画像形成方法
US7229166B2 (en) 2003-08-11 2007-06-12 Canon Kabushiki Kaisha Image-forming method, image-forming apparatus, ink set, and ink
WO2010073603A1 (fr) 2008-12-25 2010-07-01 日本化薬株式会社 Colorant à la porphyrazine, composition en contenant, et matériau coloré
JP2010196062A (ja) * 2010-03-23 2010-09-09 Fujifilm Corp フタロシアニン化合物、インク、インクジェット記録方法、および画像形成方法
CN104419222A (zh) * 2013-09-06 2015-03-18 北京联创佳艺影像新材料技术有限公司 一组适用于喷墨打印领域的高牢度的染料及其制备方法

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4632703A (en) * 1983-03-29 1986-12-30 Canon Kabushiki Kaisha Recording liquid
JPH01126381A (ja) * 1987-11-12 1989-05-18 Ricoh Co Ltd 水性インク組成物
JPH01190770A (ja) * 1988-01-26 1989-07-31 Ricoh Co Ltd 水性インク組成物
JPH05295292A (ja) * 1992-01-31 1993-11-09 Pentel Kk 液状組成物
JPH08302253A (ja) * 1995-05-10 1996-11-19 Asahi Glass Co Ltd インクジェット記録用インク
JPH11302285A (ja) * 1998-04-21 1999-11-02 Canon Inc ポルフィラジン誘導体、インク、カラーフィルタ、液晶パネル、コンピュータ及びカラーフィルタの製造方法
US5980623A (en) * 1997-01-29 1999-11-09 Fuji Xerox Co., Ltd. Ink set for ink jet recording and ink jet recording method
US6015455A (en) * 1996-08-21 2000-01-18 Fuji Xerox Co., Ltd. Ink jet recording ink and ink jet recording method
JP2001011331A (ja) * 1999-07-02 2001-01-16 Nippon Kayaku Co Ltd 新規フタロシアニン類及びカラーフィルター
WO2002008340A1 (fr) * 2000-07-26 2002-01-31 Nippon Kayaku Kabushiki Kaisha Melange de colorants cyan, composition aqueuse d'encre cyan, et procede d'inscription par jet d'encre

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4632703A (en) * 1983-03-29 1986-12-30 Canon Kabushiki Kaisha Recording liquid
JPH01126381A (ja) * 1987-11-12 1989-05-18 Ricoh Co Ltd 水性インク組成物
JPH01190770A (ja) * 1988-01-26 1989-07-31 Ricoh Co Ltd 水性インク組成物
JPH05295292A (ja) * 1992-01-31 1993-11-09 Pentel Kk 液状組成物
JPH08302253A (ja) * 1995-05-10 1996-11-19 Asahi Glass Co Ltd インクジェット記録用インク
US6015455A (en) * 1996-08-21 2000-01-18 Fuji Xerox Co., Ltd. Ink jet recording ink and ink jet recording method
US5980623A (en) * 1997-01-29 1999-11-09 Fuji Xerox Co., Ltd. Ink set for ink jet recording and ink jet recording method
JPH11302285A (ja) * 1998-04-21 1999-11-02 Canon Inc ポルフィラジン誘導体、インク、カラーフィルタ、液晶パネル、コンピュータ及びカラーフィルタの製造方法
JP2001011331A (ja) * 1999-07-02 2001-01-16 Nippon Kayaku Co Ltd 新規フタロシアニン類及びカラーフィルター
WO2002008340A1 (fr) * 2000-07-26 2002-01-31 Nippon Kayaku Kabushiki Kaisha Melange de colorants cyan, composition aqueuse d'encre cyan, et procede d'inscription par jet d'encre

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003062323A1 (fr) * 2002-01-22 2003-07-31 Fuji Photo Film Co., Ltd. Encre contenant un compose de phtalocyanine soluble dans l'eau pour impression a jet d'encre, procede d'impression a jet d'encre et procede reduisant la decoloration due a l'ozone dans une image coloree
US7219988B2 (en) 2002-01-22 2007-05-22 Fuji Photo Film Co., Ltd. Water-soluble phthalocyanine compound-containing ink for ink jetting, ink jet recording method and method for improving ozone gas discoloration of colored image material
EP1462492A1 (fr) * 2003-03-27 2004-09-29 Fuji Photo Film Co., Ltd. Encre et assortiment d'encre
US7267715B2 (en) 2003-03-27 2007-09-11 Fujifilm Corporation Ink and ink set
US7229166B2 (en) 2003-08-11 2007-06-12 Canon Kabushiki Kaisha Image-forming method, image-forming apparatus, ink set, and ink
JP2005179469A (ja) * 2003-12-18 2005-07-07 Fuji Photo Film Co Ltd フタロシアニン化合物、インク、インクジェット記録方法、および画像形成方法
JP4516744B2 (ja) * 2003-12-18 2010-08-04 富士フイルム株式会社 フタロシアニン化合物、インク、インクジェット記録方法、および画像形成方法
WO2010073603A1 (fr) 2008-12-25 2010-07-01 日本化薬株式会社 Colorant à la porphyrazine, composition en contenant, et matériau coloré
KR20110112805A (ko) 2008-12-25 2011-10-13 니폰 가야꾸 가부시끼가이샤 포르피라진 색소, 이를 함유하는 잉크 조성물 및 착색체
JP2010196062A (ja) * 2010-03-23 2010-09-09 Fujifilm Corp フタロシアニン化合物、インク、インクジェット記録方法、および画像形成方法
CN104419222A (zh) * 2013-09-06 2015-03-18 北京联创佳艺影像新材料技术有限公司 一组适用于喷墨打印领域的高牢度的染料及其制备方法

Similar Documents

Publication Publication Date Title
JP5451556B2 (ja) 色素化合物
JP2003034758A (ja) 耐酸化性銅−フタロシアニン化合物錯体水溶性染料並びにそれを用いた染料組成物及び記録液
TWI290946B (en) Cyan dye mixture, aqueous cyanic ink composition and ink-jet printing method
EP1820831B1 (fr) Encre cyan pour enregistrement à jet d'encre
CN1831054B (zh) 油墨组合物、墨盒、喷墨记录方法以及记录物
CN1654560B (zh) 油墨组合物、喷墨记录方法及记录品
JP6272096B2 (ja) 化合物、インク、インクカートリッジ、及びインクジェット記録方法
EP2327747B1 (fr) Encre à base d'eau pour enregistrement par jet d'encre, cartouche d'encre et appareil d'enregistrement par jet d'encre
JPH0613653B2 (ja) 水性インク組成物
JP2007217535A (ja) インクジェット記録用インク
JP5179448B2 (ja) アントラピリドン色素およびそれらの製法および用途
WO2002088256A1 (fr) Colorant soluble dans l'eau et resistant a l'oxydation forme d'un complexe cuivre/compose de phtalocyanine, composition de colorant contenant ce complexe et fluide de marquage
JP4658934B2 (ja) フタロシアニン類及びインクジェットプリンタにおけるその使用
ES2806080T3 (es) Colorantes bisazo y mezclas de estos
JP2016199618A (ja) インク、インクカートリッジ、及びインクジェット記録方法
JPS5974173A (ja) 赤色水性インク
JP2000265099A (ja) インクジェット記録方法
EP2843004A1 (fr) Composition colorée pour une utilisation en impression, procédé d'impression et tissu
JP2011132275A (ja) インク、インクカートリッジ及びインクジェット記録方法
JP4766228B2 (ja) インク組成物、インクカートリッジ、インクジェット記録方法及び記録物
JP5435886B2 (ja) 色素化合物並びに該色素化合物を含有するインク
TW201107423A (en) Coloring matter consisting of trisazo compound, ink compositions, recording method, and colored body
JP5212586B2 (ja) インクジェット記録用シアンインク
JPS6158503B2 (fr)
JP5440847B2 (ja) インクジェット記録用水性インク、インクカートリッジおよびインクジェット記録装置

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): DE FR GB

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase