WO2009133668A1 - Colorant phtalocyanine hydrosoluble, composition d'encre aqueuse et agent absorbant dans le proche infrarouge - Google Patents

Colorant phtalocyanine hydrosoluble, composition d'encre aqueuse et agent absorbant dans le proche infrarouge Download PDF

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Publication number
WO2009133668A1
WO2009133668A1 PCT/JP2009/001825 JP2009001825W WO2009133668A1 WO 2009133668 A1 WO2009133668 A1 WO 2009133668A1 JP 2009001825 W JP2009001825 W JP 2009001825W WO 2009133668 A1 WO2009133668 A1 WO 2009133668A1
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Prior art keywords
water
dye
formula
salt
ink composition
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English (en)
Japanese (ja)
Inventor
広田光司
藤井隆文
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Nippon Kayaku Co Ltd
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Nippon Kayaku Co Ltd
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Priority to JP2010510024A priority Critical patent/JPWO2009133668A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0083—Solutions of 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
    • C09B47/20—Obtaining compounds having sulfur 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/28—Storage stability; Improved self life

Definitions

  • the present invention relates to a water-soluble phthalocyanine dye or a salt thereof having absorption in the near infrared region, a water-based ink composition containing the same, and a near infrared absorber.
  • near-infrared absorbing dyes having absorption in the near-infrared region of 700 to 2000 nm have been studied for use in various industrial applications.
  • it is used for optical information recording media such as CD-R, for printing such as thermal CTP, flash toner fixing or laser thermal recording, and for use in a thermal barrier film.
  • it uses the characteristic of selectively absorbing light in a specific wavelength range, and is also used for a near-infrared cut filter used for a PDP filter or the like, a plant growth adjusting film, or the like.
  • It can also be used as a near-infrared absorbing ink that is made into an ink by dissolving or dispersing a near-infrared absorbing dye in a solvent and is difficult to recognize visually and can be read only by a near-infrared detector or the like. .
  • Inks are mainly classified into water-based and organic solvent-based inks depending on the main component of the solvent.
  • the use of water-based inks is strongly desired from the viewpoint of environmental issues. Development is desired.
  • an immonium dye As the near-infrared absorbing dye, an immonium dye, a diimmonium dye, a dithiol metal complex dye, a cyanine dye, and the like are known.
  • Patent Document 1 describes a cyanine dye imparted with water-solubility, but its storage stability is not practical when it is made into an aqueous solution.
  • Patent Document 2 describes a cyanine dye which imparts water solubility and has good storage stability in an aqueous solution.
  • Patent Document 4 exemplifies a number of phthalocyanine compounds having phenylthio or alkylthio as a substituent, and discloses applications such as infrared inks. However, all of those shown in the synthesis examples are organic. It is a phthalocyanine compound soluble in a solvent, and there is no disclosure about water-based ink. .
  • Patent Document 5 discloses an aqueous inkjet ink containing a near-infrared absorbing naphthalocyanine dye and gallium naphthalocyanine.
  • the present invention has been made in view of the situation as described above, and an object of the present invention is to provide a phthalocyanine dye having absorption in the near infrared region and having water solubility in a simple and low cost, An object of the present invention is to provide a water-based ink composition containing a water-soluble phthalocyanine dye and excellent in storage stability, and a near infrared absorber.
  • M represents a hydrogen atom, a metal atom, a metal oxide, a metal hydroxide, or a metal halide
  • R represents a sulfo group or a carboxy group
  • m represents an integer of 0 to 2
  • n represents an integer of 12 to 16
  • p represents an integer of 0 to 4, respectively.
  • M is Cu or VO
  • (R) m-substituted phenylthio group is an o-carboxyphenylthio group
  • n is an integer of 14 to 16
  • p is an integer of 0 to 2.
  • a water-soluble phthalocyanine dye or a salt thereof (22)
  • the water-soluble phthalocyanine dye represented by formula (1) or a salt thereof is represented by formula (1), wherein M is Cu or VO, R is a carboxy group, m is 1, n is 12 to 16, and p is 0 to 4.
  • the water-based ink composition according to the above (1) which is a water-soluble phthalocyanine dye mixture or a salt thereof in an area ratio of high performance liquid chromatography of 3 to 70%, (24) Either the dye of the formula (1) described in the above (1) or (2), the dye of the formula (2) described in the above (6), or the dye described in the formula (101) described in the above (9)
  • a near-infrared absorber containing at least one of at least one kind of dye having at least one hydroxy group and one kind of dye having no hydroxy group.
  • the water-soluble phthalocyanine dye represented by the above formula (1) or a salt thereof used in the present invention absorbs near infrared rays, has excellent solubility in water and water-soluble organic solvents, and the dye is dissolved in an aqueous solvent. It can be set as the ink composition (aqueous ink composition) in an aqueous solution.
  • the aqueous ink composition of the present invention containing this coloring matter has very good storage stability without solid precipitation, physical property change, hue change and the like after long-term storage.
  • the present invention will be described in detail.
  • the “dye of the present invention” including both of “the dye of the present invention or a salt thereof” will be simply described below.
  • descriptions of “a dye represented by Formula (1)”, “a dye represented by Formula (2)”, “a dye represented by Formula (101)”, and the like are not particularly refused.
  • the “dye of the present invention” means the “dye represented by the formula (1)”, the “dye represented by the formula (2)”, and the “dye represented by the formula (101), unless otherwise specified.
  • the aqueous ink composition of the present invention is characterized by containing the coloring matter of the present invention.
  • M represents a hydrogen atom, a metal atom, a metal oxide, a metal hydroxide, or a metal halide
  • R represents a sulfo group or a carboxy group
  • m represents an integer of 0 to 2
  • n represents an integer of 12 to 16
  • p represents an integer of 0 to 4, respectively.
  • the sum of n and p is 16 at maximum.
  • Said M represents a hydrogen atom, a metal atom, a metal oxide, a metal hydroxide, or a metal halide.
  • M is other than a hydrogen atom
  • the M is a so-called central metal of a phthalocyanine dye. Therefore, when M is a monovalent metal cation, it means that the central metal is two molecules, and when M is a divalent metal cation, the central metal is one molecule.
  • M is a hydrogen atom
  • the phthalocyanine dye represented by the formula (1) does not have a central metal, which means that two nitrogen atoms bonded to M each have one hydrogen atom.
  • metal atoms include, for example, 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, and Bi.
  • metal oxide include VO and GeO.
  • metal hydroxide include Si (OH) 2 , Cr (OH) 2 , Sn (OH) 2, and AlOH.
  • the metal halide for example, SiCl 2, VCl, VCl 2 , VOCl, FeCl, GaCl, ZrCl and AlCl like.
  • M in the formula (1) is preferably Fe, Co, Cu, Ni, Zn, Al, AlOH, V or VO, more preferably Fe, Co, Cu, Ni, Zn, Al or VO. More preferably, Cu or VO is mentioned.
  • R represents a sulfo group or a carboxy group, and a carboxy group is preferable.
  • the sulfo group or carboxy group may be a free acid or a salt thereof.
  • the water-soluble phthalocyanine dye of formula (1) is a salt
  • the sulfo group or carboxy group forms a salt.
  • the salt may be a water-soluble salt, and examples thereof include alkali metal salts such as sodium salt and potassium salt; ammonium salt: and lower alkyl ammonium salt such as tetramethylammonium salt. Alkali metal salts are more preferable in terms of water solubility.
  • the substitution position of R is not particularly limited, but the 2-position is preferred when the substitution position of the sulfur atom is the 1-position. More preferred R includes a 2-carboxy group.
  • n represents an integer of 0 to 2, preferably 1 or 2, and more preferably 1.
  • the number of sulfo groups and / or carboxy groups represented by R is usually about 12 to 20 per molecule, preferably about 12 to 16 per molecule, and more preferably one molecule. The number is about 14 to 16.
  • n represents an integer of 12 to 16. In order to obtain high water solubility, a larger value is advantageous. Therefore, n is preferably 14 to 16.
  • p represents an integer of 0 to 4. In some cases, 1 to 3 is preferable, 1 to 2 is more preferable, and 1 is more preferable. Usually, p is preferably 0 to 2. In particular, when the central metal is VO, p is preferably 0 to 2, and when it is a metal such as Cu other than VO, p is more preferably 0 or 1.
  • n is 12 to 16, preferably 14 to 16, and when n is smaller than 16, the difference between 16 and the numerical value (value of n) is the number of substitutions with a hydrogen atom or / and a hydroxy group. It is.
  • n is 15 or 14
  • the remaining site on the benzene ring when n is 15, the remaining site is 1 and when n is 14, the remaining site is 2): A hydrogen atom or / and a hydroxy group.
  • the number of substituents of the hydroxy group is represented by p in the above formula (1), and p is 0 to 4, preferably 0 to 2.
  • the number obtained by subtracting the number substituted with a hydroxy group and a phenylthio group from 16 of the total number of positions having substituents on the four benzene rings of the phthalocyanine ring in the formula (1) is the number on the benzene ring.
  • the number of unsubstituted hydrogen atoms is 16- (2-carboxyphenylthio group number + q) and 16- (2-carboxyphenylthio group, respectively.
  • Number + r the total of n and p in the formula (1) is 16.
  • the total of the number of 2-carboxyphenylthio groups and q or r is 16 at maximum.
  • the dye represented by formula (1) is a mixture of positional isomers with respect to substitution positions of substituents on the four benzene rings of the phthalocyanine ring. It is extremely difficult to specify the position of substitution of the regioisomer, and even if it is a mixture of regioisomers, the effect of the present invention is not harmed. Therefore, the dye of the present invention also contains the regioisomer described above. .
  • the ink composition of the present invention contains at least one dye represented by the formula (1).
  • at least two kinds of the dyes are contained. It is easier to synthesize the dye represented by the formula (1) as a mixture than as a single compound. Usually, even if this pigment
  • the dye mixture containing at least two kinds of the dye of the present invention in the formula (1), a mixture of different n dyes (compounds having different numbers of substitutions of (R) m-substituted phenylthio groups), or the formula (2) or In the formula (101), a mixture of dyes having different numbers of substitutions of 2-carboxyphenylthio groups, for example, preferably, the number of substitutions of the (R) m-substituted or 2-carboxy-substituted phenylthio groups is 14,15 And a dye mixture containing three kinds of dyes of No.
  • n 1 to 4, preferably 1 to 2
  • q in the formula (2) is 1 to 2
  • r in the formula (101) is 1 to 2
  • the ratio of the dye having a hydroxy group is the area ratio by high-speed chromatography (HPLC) with respect to the total amount of the dye mixture, It is preferably 3 to 70%, and the balance (97 to 30%) is the proportion of the dye having no hydroxy group.
  • the ratio of the dye having a hydroxy group is more preferably 30 to 60% in the above area ratio.
  • the proportion of the dye having a hydroxy group is 3 to 20%, preferably in the above area ratio. 4 to 10%.
  • the hydroxy number of the dye having a hydroxy group may be any of 1 to 4. Moreover, the mixture in which the number of hydroxy groups differs may be sufficient, and a single compound may be sufficient.
  • the dye having a hydroxy group is preferably a dye having one or two hydroxy groups. Accordingly, a dye mixture of a dye having one or two hydroxy groups and a dye not having a hydroxy group is more preferable.
  • the ratio of the dye having a hydroxy group in the dye mixture to the entire dye mixture is preferably 3 to 70%, and the balance (97 to 30%) is the ratio of the dye having no hydroxy group.
  • a near-infrared absorber containing, as an active ingredient, a dye mixture of a dye having a hydroxy group and a dye having no hydroxy group is one aspect of the present invention.
  • the content of the pigment mixture in the near infrared absorber is not particularly limited as long as it is an amount that plays a role as a near infrared absorber.
  • the content of the dye mixture is in the range of 0.01 to 100%, preferably 0.05 to 100%, based on the total amount of the near infrared absorber.
  • the near-infrared absorber can optionally contain additives other than the active ingredient.
  • the optional additive may be any additive as long as it is used for a near infrared absorber.
  • the content of the optional additive is in the range of 0 to 99.99%, preferably 0 to 99.95%, based on the total amount of the near infrared absorber.
  • the optional additive include water and an aqueous solvent.
  • the near-infrared absorber of the present invention can be an aqueous near-infrared absorber containing water in which the above active ingredients are dissolved.
  • a preferred example thereof is the water-based ink composition of the present invention described later.
  • the number of phenylthio groups in the dye of the present invention used in the present invention is usually 12 to 16, more preferably 14 to 16.
  • the total number of phenylthio groups and hydroxy groups is 16.
  • the dye of the present invention used in the present invention may be a single compound having the same number of substituents of phenylthio group and hydroxy group or a mixture having different numbers of substituents. A mixture of two or more is preferred. In particular, a dye mixture of a dye having a hydroxy group and a dye having no hydroxy group is more preferable.
  • n is a dye mixture composed of a dye represented by 16, 15 or 14
  • a preferable mixing ratio of each dye to the total amount of the dye mixture is HPLC.
  • area ratio 16: 20 to 65%
  • n 15: 10 to 55%
  • n 14: 0 to 30%, preferably 6 to 30%.
  • the mixing ratio of each dye to the total amount of the dye mixture is an HPLC area ratio, and usually n is 16:34 to 64% / n is 15:12.
  • To 52% / n 14: 0 to 28%, preferably 39 to 59% / 25 to 47% / 3 to 23%, and more preferably 44 to 54% / n respectively. 30 to 42% / 8 to 18%.
  • the dye represented by the formula (2) is the dye represented by the formula (2).
  • q represents an integer of 0 to 2, preferably 0 or 1, more preferably 1.
  • 14 to 16 represents an integer of 14 to 16, and the sum total with q is 16.
  • the dye represented by the formula (2) is also preferably a dye mixture containing at least two kinds of the dye represented by the formula (2) as in the case of the dye of the formula (1).
  • one preferred as in the formula (2) is a dye represented by the formula (101).
  • r represents an integer of 0 to 2, preferably 1.
  • “14 to 16” indicates any integer of 14 to 16, and the total of r is 16 at the maximum.
  • the dye represented by the formula (101) is also preferably a dye mixture containing at least two kinds of dyes selected from the dye represented by the formula (101) as in the formula (1). .
  • M is VO
  • the mixing ratio of each dye when n is a mixture of dyes represented by 16, 15 and 14 is slightly different from that in which M is other than VO.
  • the mixing ratio with respect to the total amount of the dye of the present invention is HPLC area ratio
  • n 16:12 to 42% / n is 15:29 to 59% / n is 14: 4 to 34%, preferably ,
  • M As for M, R, m, n and p in the formula (1), a combination of preferable ones is more preferable, and a combination of more preferable ones is more preferable. The same applies to preferable ones.
  • Specific examples of preferred dyes of the present invention and water-based inks containing the same are as follows.
  • the dye of the present invention basically includes a halogenophthalocyanine having a halogen atom corresponding to the number of substitutions (n) of the (R) m-substituted phenylthio group in the formula (1) on the benzene ring of the phthalocyanine skeleton.
  • a halogenophthalocyanine having a halogen atom corresponding to the number of substitutions (n) of the (R) m-substituted phenylthio group in the formula (1) on the benzene ring of the phthalocyanine skeleton.
  • a compound in which n is 14 to 16 in the formula (1) is obtained.
  • R is a sulfo group
  • after making the compound represented by following formula (3) and the compound represented by following formula (4) whose m is 0 react by a conventional method For example, it can also be obtained by sulfonation using fuming sulfuric acid or the like.
  • the compounds represented by the following formulas (3) and (4) can be synthesized by a known method, but can also be purchased as a commercial product.
  • reaction of the compound represented by the formula (3) and the compound represented by the formula (4) is performed in the same manner as in a normal nucleophilic substitution reaction, such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and / Or in the presence of a base such as sodium hydride.
  • a normal nucleophilic substitution reaction such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and / Or in the presence of a base such as sodium hydride.
  • This reaction is usually preferably carried out in a solvent.
  • aprotic polar solvents such as N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N, N′-dimethylimidazolidinone (DMI), sulfolane; acetone, methyl isobutyl
  • ketone solvents such as ketones
  • aromatic hydrocarbon solvents such as toluene, xylene and dichlorobenzene.
  • a base is added to the compound represented by the formula (3) by 16 to 52 times equivalent, preferably 24 to 52 times equivalent of the compound, and dissolved in a solvent of 20 to 30 times weight of the compound with stirring.
  • the mixture is suspended, and then the compound represented by the formula (4) is added thereto in an amount of 16 to 32 times equivalent, preferably 16 to 25 times equivalent to the compound represented by the formula (3).
  • the reaction is carried out at 80 to 150 ° C., preferably 110 to 140 ° C.
  • the reaction may be performed under normal pressure or under pressure.
  • the reaction time varies depending on the reaction conditions, but is usually in the range of 1 to 50 hours.
  • the progress of the reaction can be confirmed, for example, by measuring ⁇ max (maximum absorption wavelength) of the reaction solution.
  • the precipitated solid is separated by filtration, washed with water or alcohol as necessary, the inorganic salt contained as an impurity in the dye, unreacted raw materials, etc. are removed and then dried.
  • the dye represented by the formula (1) can be obtained. You may refine
  • dye represented by Formula (2) or Formula (101) of this invention can be manufactured similarly by using thiosalicylic acid or its salt as a thiol compound represented by the said Formula (4). it can.
  • the coloring matter of the present invention is suitable for dyeing natural and synthetic fiber materials or blended products, and also for producing water-based ink compositions for writing ink and inkjet recording.
  • the solution containing the dye represented by the formula (1) of the present invention for example, the reaction solution in the final step in the synthesis reaction of the dye, can also be directly used for the production of the aqueous ink composition of the present invention.
  • the dye is isolated from a solution containing the dye of the present invention such as a reaction solution, for example, the dye is isolated by a method such as drying after filtration separation or spray drying of the solution, and then the obtained dye is used as an ink. It can also be processed into a composition.
  • the coloring matter of the present invention is usually 0.05 to 20% by mass, preferably 0.05 to 10% by mass, more preferably 0.05 to 10% by mass based on the total amount of the water-based ink composition. 5% by mass, more preferably 0.05 to 1% by mass.
  • the dye of the present invention is usually contained in an aqueous solution in an amount of 0.1 to 20% by mass, more preferably 0.1 to 10% by mass, and still more preferably 0.1 to 5% by mass.
  • the balance is an additive such as water and a water-soluble organic solvent which may optionally be added.
  • the water-soluble organic solvent is usually contained in the range of 0 to 60% by mass with respect to the total amount of the ink composition.
  • the pigment used in the ink composition of the present invention preferably has a higher content of the pigment of the present invention or a pigment mixture of the pigment (purity of the pigment of the present invention) in the pigment.
  • the preferable content is usually 80% or more, preferably 85% or more, more preferably 90% or more, and further preferably 95% or more. Only the dye represented or a mixture of the dyes (purity 100%) may be used.
  • a preferable water-based ink composition of the present invention is a case where the dye described in any one of (i) to (xii) is contained as the dye represented by the formula (1).
  • the dye of the present invention (the dye represented by the formula (1)) is added with water and, if necessary, a water-soluble organic solvent (an organic solvent miscible with water). It is dissolved in an aqueous medium such as a mixed solvent (water alone or a solvent mainly composed of water), and an ink preparation agent is added as necessary.
  • aqueous medium refers to water alone or an aqueous organic solvent solution obtained by adding a water-soluble organic solvent to water.
  • the coloring matter of the present invention used for preparing the ink is a metal cation chloride contained as an impurity, such as sodium chloride; or a sulfate, such as sodium sulfate; Those having a small content of inorganic substances such as are preferred.
  • the total content of sodium chloride and sodium sulfate occupying most of the impurities contained in the dye of the present invention is preferably about 1% by mass or less in the total mass of the dye contained in the ink.
  • a method using a reverse osmosis membrane known per se, or a dried product or wet cake of the pigment of the present invention or a salt thereof in a mixed solvent of alcohol such as methanol and water for example, a method using a reverse osmosis membrane known per se, or a dried product or wet cake of the pigment of the present invention or a salt thereof in a mixed solvent of alcohol such as methanol and water.
  • combined above should just be desalted by methods, such as stirring and carrying out suspension refinement
  • the water-based ink composition of the present invention is prepared using water as a medium, and if necessary, a water-soluble organic solvent may be contained within a range that does not impair the effects of the present invention.
  • the water-soluble organic solvent is used for the purpose of functions such as dye dissolution, drying prevention (wetting), viscosity adjustment, penetration promotion, surface tension adjustment, and defoaming.
  • the water-based ink composition of the present invention preferably contains a water-soluble organic solvent.
  • ink preparation agents include, for example, antiseptic / antifungal agents, pH adjusting agents, chelating reagents, rust preventing agents, UV absorbers, viscosity adjusting agents, dye dissolving agents, antifading agents, emulsion stabilizers, surface tension adjusting agents. , Known additives such as antifoaming agents, dispersants, and dispersion stabilizers.
  • the content of the water-soluble organic solvent is 0 to 60% by mass, preferably 10 to 50% by mass with respect to the entire ink composition, and other ink preparation agents are 0 to 20% by mass with respect to the entire ink composition. It is preferable to use 0 to 15% by mass. The remainder other than the above is water.
  • water-soluble organic solvents examples include C1-C4 alkanols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol and tert-butanol; N, N-dimethyl Amides such as formamide and N, N-dimethylacetamide; 2-pyrrolidone, N-methyl-2-pyrrolidone, hydroxyethyl-2-pyrrolidone, 1,3-dimethylimidazolidin-2-one and 1,3-dimethylhexa Heterocyclic ketones such as hydropyrimido-2-one; ketones or ketoalcohols such as acetone, methyl ethyl ketone or 2-methyl-2-hydroxypentan-4-one; cyclic ethers such as tetrahydrofuran and dioxane; ethylene glycol, 1, 2- or 1,3-propi C
  • the water-soluble organic solvent mentioned above contains substances that are solid at room temperature, such as trimethylolpropane, but these are water-soluble even when they are solid, and when dissolved in water Since it can be used for the same purpose as the water-soluble organic solvent, it is described in the category of the water-soluble organic solvent in this specification for convenience.
  • water-soluble organic solvent Preferred as the water-soluble organic solvent are isopropanol, glycerin, mono-, di- or triethylene glycol, dipropylene glycol, 2-pyrrolidone, N-methyl-2-pyrrolidone and butyl carbitol, more preferably isopropanol, Glycerin, diethylene glycol, 2-pyrrolidone, N-methyl-2-pyrrolidone and butyl carbitol. These water-soluble organic solvents are used alone or in combination.
  • antiseptic / antifungal agents examples include organic sulfur, organic nitrogen sulfur, organic halogen, haloallylsulfone, iodopropargyl, N-haloalkylthio, benzothiazole, nitrile, pyridine, 8- Oxyquinoline, isothiazoline, dithiol, pyridine oxide, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiadiazine, anilide, adamantane, dithiocarbamate, brominated indanone And benzyl bromacetate compounds.
  • Examples of the organic halogen compound include sodium pentachlorophenol
  • examples of the pyridine oxide compound include sodium 2-pyridinethiol-1-oxide
  • examples of the isothiazoline compound include 1,2-benzisothiazoline.
  • Examples thereof include magnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-one calcium chloride, and 2-methyl-4-isothiazolin-3-one calcium chloride.
  • antiseptic / antifungal agents include sodium acetate, sodium sorbate, sodium benzoate and the like.
  • Specific examples of the antiseptic / antifungal agent include, for example, Proxel RTM GXL (S) and Proxel RTM XL-2 (S) (trade names, both manufactured by Avecia). In the present specification, the superscript “RTM” means a registered trademark.
  • any substance can be used as long as it can control the pH of the ink within the range of 6.0 to 11.0 for the purpose of improving the storage stability of the ink.
  • alkanolamines such as diethanolamine and triethanolamine
  • hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide
  • ammonium hydroxides or alkali metals such as lithium carbonate, sodium carbonate and potassium carbonate And carbonates thereof.
  • the pH range of the ink composition of the present invention is generally 6.0 to 11.0, preferably 7.0 to 11.0, and more preferably 8.0 to 11.0.
  • the pH range of the ink composition of the present invention is preferably the above range.
  • Examples of the chelating reagent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, and sodium uracil diacetate.
  • rust preventive examples include acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite.
  • UV absorber for example, benzophenone compounds, benzotriazole compounds, cinnamic acid compounds, triazine compounds, and stilbene compounds can be used.
  • viscosity modifier examples include water-soluble polymer compounds in addition to water-soluble organic solvents, such as polyvinyl alcohol, cellulose derivatives, polyamines, and polyimines.
  • dye solubilizer examples include urea, ⁇ -caprolactam, and ethylene carbonate. It is preferred to use urea.
  • the anti-fading agent is used for the purpose of improving image storage stability.
  • various organic and metal complex antifading agents can be used.
  • organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, and heterocycles. Includes nickel complexes and zinc complexes.
  • Examples of the surface tension adjusting agent include surfactants, and examples thereof include anionic surfactants, amphoteric surfactants, cationic surfactants, and nonionic surfactants.
  • anionic surfactants include alkyl sulfocarboxylates, ⁇ -olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acyl amino acids and salts thereof, N-acyl methyl taurate, alkyl sulfate polyoxyalkyl ethers Sulfate, alkyl sulfate polyoxyethylene alkyl ether phosphate, rosin acid soap, castor oil sulfate ester, lauryl alcohol sulfate ester, alkylphenol type phosphate ester, alkyl type phosphate ester, alkylaryl sulfonate, diethylsulfosuccinate Salts, diethylhexylsylsulfosuccinate, and dioctylsulfosuccinate.
  • cationic surfactants examples include 2-vinylpyridine derivatives and poly-4-vinylpyridine derivatives.
  • Amphoteric surfactants include lauryl dimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine, and other imidazolines. There are derivatives.
  • Nonionic surfactants include ethers such as polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether and polyoxyethylene alkyl ether; Ester systems such as polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate and polyoxyethylene stearate; 2 4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol and 3,5 Dimethyl-1-hexyne-3-acetylene glycols such as ol (alcohol) based (e.g., Nissin Chemical Industry Co., Ltd.
  • antifoaming agent highly oxidized oil-based, glycerin fatty acid ester-based, fluorine-based, and silicone-based compounds are used as necessary.
  • the surface tension of the ink composition of the present invention is usually 25 to 70 mN / m, more preferably 25 to 60 mN / m.
  • the viscosity of the ink composition of the present invention is preferably 30 mPa ⁇ s or less, and more preferably adjusted to 20 mPa ⁇ s or less.
  • water to be used is preferably water with few impurities such as ion exchange water or distilled water.
  • the prepared ink composition may be subjected to microfiltration using a membrane filter or the like, if necessary, to remove impurities, and is preferably subjected to microfiltration when used as an ink for an ink jet printer.
  • the pore size of the filter used for microfiltration is usually 1 ⁇ m to 0.1 ⁇ m, preferably 0.8 ⁇ m to 0.1 ⁇ m.
  • the aqueous ink composition containing the coloring matter of the present invention is suitable for use in printing, copying, marking, writing, drafting, stamping, or recording (printing), particularly in inkjet recording.
  • the aqueous ink composition of the present invention has high storage stability and little change in quality such as deterioration in absorbance even when left for a long period of time.
  • the recorded matter of the present invention is a substance recorded with the dye of the present invention.
  • the material of the recorded material is not particularly limited, and any information recording sheet such as paper or film, fiber or cloth (cellulose, nylon, wool, etc.) may be used. It is not limited to these.
  • the information transmission sheet is not particularly limited, and is not only plain paper but also surface-treated, specifically, paper, synthetic paper, or a substrate such as a film provided with an ink receiving layer. Can also be used.
  • the ink receiving layer is formed by, for example, impregnating or coating the base material with a cationic polymer; or inorganic fine particles capable of absorbing pigments in the ink, such as porous silica, alumina sol, or special ceramics, with polyvinyl alcohol and / or Alternatively, it is provided by a method of coating the surface of the substrate together with a hydrophilic polymer such as polyvinylpyrrolidone.
  • Those provided with such an ink receiving layer are usually called ink jet exclusive paper, ink jet exclusive film, glossy paper, or glossy film.
  • a container filled with the water-based ink composition of the present invention is set at a predetermined position of an ink jet printer, The method may be performed by ejecting small droplets in accordance with a recording signal, attaching the droplets to a recording material, and recording on the recording material.
  • the ink jet printer include a piezo method using mechanical vibration; and a bubble jet RTM method using bubbles generated by heating.
  • the ink jet recording method of the present invention can be used with any type of printer.
  • the dye of the present invention synthesized in Examples was a mixture of dyes represented by the above formula (1) as described below.
  • the synthesized dyes of the present invention all showed a solubility of 100 g / L or more in water at room temperature (25 ° C.).
  • the pH of the aqueous solution was 8-10.
  • Example 1 Synthesis of a dye represented by the following formula (2). In addition, q in a following formula shows 0 or 1.
  • this dye was a mixture of dyes of the following formulas (8) to (11), and the HPLC purity of the obtained mixture was 99.15% in terms of the total amount of each dye.
  • n and q of the dye were determined by mass spectrometry using LC-MS (LC: HP-1100, manufactured by Agilent / MS: LCT mass spectrometer, manufactured by Micromass).
  • the HPLC measurement conditions are as follows. Column: Inertsil RTM ODS-2 (5 ⁇ m, 2.1 ⁇ 250 mm) [manufactured by GL Sciences Inc.] Column oven: 40 ° C Elution solvent: 5 mM ammonium acetate / acetonitrile [95/5 (0 min) ⁇ 50/50 (30 min) ⁇ 20/80 (10 min)] Flow rate: 0.2mL / min Detector: PDA (220-900nm)
  • the dye represented by the above formula (10) is a dye in which M is Cu, R is 2-carboxy, m is 1, n is 15, and p is 1.
  • Example 2 (Preparation of water-based ink composition and storage stability test)
  • the water-based ink composition of the present invention was prepared by dissolving 0.1 part of the phthalocyanine dye of the present invention obtained in Example 1 in 100 parts of water.
  • the water used was ion exchange water.
  • the prepared water-based ink composition was left in an oven at 50 ° C. for 13 days, and a storage stability test was conducted. Before and after the test, the water-based ink composition was measured with a spectrophotometer (UV-3150, manufactured by Shimadzu Corporation), and storage stability was evaluated from the change in absorbance at the maximum absorption wavelength. The results are shown in Table 1 below.
  • Comparative Example 1 For comparison, a water-based ink composition was prepared and storage stability was evaluated in the same manner as in Example 2 except that a cyanine dye represented by the following formula (7) was used instead of the dye. This is referred to as Comparative Example 1. The results are shown in Table 1 below. In addition, the pigment
  • the obtained solid was suspended in 80 parts of water, and then the suspension was adjusted to pH 9.5 with 25% aqueous sodium hydroxide solution to dissolve the solid. Thereto was added 200 parts of 2-propanol, and the precipitated solid was separated by filtration and dried to obtain 2.8 parts of a sodium salt of the dye of the present invention represented by the above formula (101).
  • the obtained dye is a mixture of dyes of the following formulas (102) to (105), and the HPLC purity of the obtained dye is determined by the above-mentioned dyes. The total amount was 90.38%.
  • n and r of each dye were determined by mass spectrometry using LC-MS (LC: ACQUITY UPLC RTM , manufactured by Waters / MS: LCT mass spectrometer, manufactured by Micromass).
  • the HPLC measurement conditions are as follows. Column: ACQUITY UPLC RTM BEH Shield RP18 (1.7 ⁇ m, 2.1 ⁇ 100 mm) [manufactured by Waters] Column oven: 40 ° C Elution solvent: 5 mM ammonium acetate / acetonitrile [95/5 (0 min) ⁇ 50/50 (10 min) ⁇ 50/50 (12 min)] Flow rate: 0.35 mL / min Detector: PDA (220-800nm)
  • the dyes represented by the above formulas (102) and (104) are represented by the formula (1), in which M is VO, R is 2-carboxyl, with the substitution position of the sulfur atom being the 1-position, m is 1, and n is Each of 16 and 15, and p is a dye represented by 0.
  • the dye represented by the above formula (103) is a dye in which M is VO, R is 2-carboxy, m is 1, n is 15, and p is 1.
  • the dye represented by the formula (105) is a dye represented by M is VO, R is 2-carboxy, m is 1, n is 14, and p is 2.
  • Example 4 Water-based ink composition and storage stability test
  • the dye residual ratio in the ink composition was 48%.
  • the phthalocyanine dye of the present invention obtained in Example 3 has a high dye residual ratio of 48% as compared with the residual ratio of the dye of Comparative Example 1. It can be seen that the storage stability is extremely superior compared to the other dyes.
  • the water-soluble phthalocyanine dye of the present invention or a salt thereof is excellent in solubility in water or a water-soluble organic solvent.
  • the aqueous ink composition of the present invention containing this coloring matter has very good storage stability without solid precipitation, physical property change, hue change, etc. after long-term storage. Therefore, the water-based ink composition of the present invention is suitably used for printing, copying, marking, writing, drafting, stamping, recording (printing), etc., and particularly suitably used as a near infrared absorbing ink for inkjet recording. It is done.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Ink Jet (AREA)

Abstract

Cette invention concerne un colorant phtalocyanine hydrosoluble représenté par la formule générale (1), ou un de ses sels (1) (dans la formule, M représente un atome métallique ou autre atome similaire, R représente un groupe sulfo ou un groupe carboxy, m représente un nombre entier entre 0 et 2, n représente un nombre entier entre 12 et 16, et p représente un nombre entier entre 0 et 4), et une composition d'encre aqueuse contenant au moins ledit colorant ou sel de celui-ci. Selon l'invention, il est possible de proposer simplement et à bas coût un colorant phtalocyanine qui absorbe la lumière dans le proche infrarouge et est exceptionnellement hydrosoluble, et de proposer une composition d'encre aqueuse ayant une exceptionnelle stabilité en stockage et contenant ledit colorant.
PCT/JP2009/001825 2008-04-28 2009-04-22 Colorant phtalocyanine hydrosoluble, composition d'encre aqueuse et agent absorbant dans le proche infrarouge Ceased WO2009133668A1 (fr)

Priority Applications (1)

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JP2013108060A (ja) * 2011-10-26 2013-06-06 Yamada Chem Co Ltd フタロシアニン化合物、近赤外吸収色素及び近赤外吸収材
WO2013132718A1 (fr) * 2012-03-07 2013-09-12 富士フイルム株式会社 Composition colorée pour une utilisation en impression, procédé d'impression et tissu
JP2014062142A (ja) * 2012-09-19 2014-04-10 Fujifilm Corp インクセット、捺染方法、及び布帛
WO2014168221A1 (fr) * 2013-04-11 2014-10-16 富士フイルム株式会社 Composition absorbant les rayons proche infrarouge, filtre de coupure de rayon proche infrarouge l'utilisant, procédé de fabrication de celui-ci, module de caméra, et procédé de fabrication de celui-ci
JPWO2014115692A1 (ja) * 2013-01-22 2017-01-26 山田化学工業株式会社 フタロシアニン化合物、近赤外線吸収色素及び近赤外線吸収材料

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022024926A1 (fr) * 2020-07-31 2022-02-03 住友化学株式会社 Composés

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JPH048771A (ja) * 1990-04-27 1992-01-13 Nippon Shokubai Co Ltd フタロシアニン化合物の製造方法
JPH07247454A (ja) * 1992-01-25 1995-09-26 Basf Ag 印刷インキ
JP2001213884A (ja) * 2000-01-31 2001-08-07 Yamada Chem Co Ltd 水溶性フタロシアニン化合物

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JPH048771A (ja) * 1990-04-27 1992-01-13 Nippon Shokubai Co Ltd フタロシアニン化合物の製造方法
JPH07247454A (ja) * 1992-01-25 1995-09-26 Basf Ag 印刷インキ
JP2001213884A (ja) * 2000-01-31 2001-08-07 Yamada Chem Co Ltd 水溶性フタロシアニン化合物

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013108060A (ja) * 2011-10-26 2013-06-06 Yamada Chem Co Ltd フタロシアニン化合物、近赤外吸収色素及び近赤外吸収材
WO2013132718A1 (fr) * 2012-03-07 2013-09-12 富士フイルム株式会社 Composition colorée pour une utilisation en impression, procédé d'impression et tissu
JP2014062219A (ja) * 2012-03-07 2014-04-10 Fujifilm Corp 捺染用着色組成物、捺染方法、及び布帛
CN104169371A (zh) * 2012-03-07 2014-11-26 富士胶片株式会社 印染用着色组合物、印染方法及布帛
JP2014062142A (ja) * 2012-09-19 2014-04-10 Fujifilm Corp インクセット、捺染方法、及び布帛
JPWO2014115692A1 (ja) * 2013-01-22 2017-01-26 山田化学工業株式会社 フタロシアニン化合物、近赤外線吸収色素及び近赤外線吸収材料
WO2014168221A1 (fr) * 2013-04-11 2014-10-16 富士フイルム株式会社 Composition absorbant les rayons proche infrarouge, filtre de coupure de rayon proche infrarouge l'utilisant, procédé de fabrication de celui-ci, module de caméra, et procédé de fabrication de celui-ci
US9826129B2 (en) 2013-04-11 2017-11-21 Fujifilm Corporation Near-infrared-ray-absorbing composition, near-infrared-ray cut filter using same, manufacturing method therefor, camera module, and manufacturing method therefor

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