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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
  • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
  • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
  • B41J2/01—Ink jet
• • 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
  • 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
• • 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
  • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
• • 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
  • C09B67/006—Preparation of organic pigments
• • 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
  • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes

Definitions

• the present invention relates to a dye ink composition, a dye ink for inkjet recording, and an inkjet recording method.
• the inkjet recording method is cheaper in material cost, capable of high-speed recording, less noise during recording, simpler in process, easier to full-color, and simpler. It has become widespread because it has the advantage of being able to obtain high-resolution images even with devices with various configurations, and is expanding from personal to office applications, commercial printing, and industrial printing.
• Patent Documents 1 to 4 As a colorant for cyan dye ink, compounds having a phthalocyanine skeleton are known (Patent Documents 1 to 4).
• a general-purpose plain paper having a low water absorption capacity or the like may be used in addition to an inkjet paper or a glossy paper for an inkjet having an ink receiving layer.
• plain paper is mainly used as a recording medium, and high image density is required.
• Such a material to be recorded does not positively include an absorbing layer, and ink does not easily permeate into the material to be recorded, so that a large amount of time is spent for drying.
• an inkjet recording method that dries quickly, has a high image density, and has high image quality and high durability even for a material to be recorded that does not have an ink receiving layer such as plain paper has been longed for.
• a phthalocyanine skeleton for example, CI Direct Blue 86, 87, 199
• CI Direct Blue 86, 87, 199 which are widely used for cyan dye ink applications
• a recording medium inkprint paper
• an ink receiving layer formed of an inorganic substance such as alumina or silica
• the compound having a triphenylmethane skeleton is characterized in having excellent color development property as compared with the compound having a phthalocyanine skeleton.
• Patent Document 1 A cyan ink containing a compound having a triphenylmethane skeleton such as acid blue 9 as a coloring material has been proposed (Patent Document 1).
• Patent Document 1 the cyan dye ink of Patent Document 1 cannot realize both print density (color development) and image durability (ozone resistance and light resistance), and further improvement is required.
• Patent Document 2 Two requirements, mainly by changing the colorant (dye) for cyan dye ink, in order to break the trade-off relationship between print density (color development) and image durability (ozone resistance and light resistance). Proposals have been made to achieve both performance (Patent Document 2 and Patent Document 3).
• the cyan dye ink of Patent Document 2 can confirm the improvement of the printing density (color development), the image durability (ozone resistance: yellow discoloration) on the inkjet paper derived from the partial azaphthalocyanine compound is lowered.
• Decreased image durability (ozone resistance: decolorization) on inkjet paper derived from phthalocyanine compound C.I. I.
• the cyan dye ink of Patent Document 4 has improved photographic density (color development) and image fastness (ozone resistance) on inkjet paper, the photographic density on plain paper derived from a partial azaphthalocyanine compound can be confirmed. Turned out to be room for improvement.
• An object of the present invention is a dye ink composition capable of forming an image having excellent printing density (particularly, color development on plain paper) and excellent ozone resistance and light resistance, a dye ink for inkjet recording, and a dye ink for inkjet recording.
• the purpose is to provide an inkjet recording method.
• the present inventors have found that the above object can be achieved by the following configuration.
• Q 1 , P 1 , W 1 , S 1 , Q 2 , P 2 , W 2 , S 2 , Q 3 , P 3 , W 3 , S 3 , Q 4 , P 4 , W 4 , and S 4 respectively.
• R 1 represents a hydrogen atom or a substituent.
• Ring A formed from Q 1 , P 1 , W 1 , and S 1 .
• Q 2, P 2, W 2 , and ring B formed from S 2 Ring C formed from Q 3 , P 3 , W 3 , and S 3 , and Q 4, P 4, W 4 , and ring D formed from S 4 represent each independently a substituted or unsubstituted benzene ring, or a 6-membered nitrogen-containing heterocyclic ring substituted or unsubstituted.
• the remaining one ring is a substituted or unsubstituted pyridine ring, substituted or unsubstituted.
• ring A a substituted or unsubstituted pyrimidine ring
• ring D a substituted or unsubstituted pyridazine ring
• the remaining two rings are independently substituted or unsubstituted pyridine rings, respectively.
• Substituted or unsubstituted pyrazine ring, substituted or unsubstituted pyrimidine ring, or substituted or unsubstituted pyridazine ring substituted or unsubstituted pyridazine ring.
• Ring A, Ring B, Ring C and Ring D if one ring represents a substituted or unsubstituted benzene ring, the remaining three rings are independently substituted or unsubstituted pyridine rings, respectively. , Substituted or unsubstituted pyrazine ring, substituted or unsubstituted pyrimidine ring, or substituted or unsubstituted pyridazine ring. Ring A, Ring B, Ring C and Ring D do not all represent simultaneously substituted or unsubstituted benzene rings.
• the dye represented by the general formula (I) has at least one ionic hydrophilic group as a substituent.
• 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.
• 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.
• At least one of the rings A, B, C and D in the dye represented by the general formula (I) is a group selected from -SO 2- Z, -SO 3 M, and -CO 2 M.
• M represents a hydrogen atom or a counter cation.
• Z represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.
• One to three of P 1 , W 1 , P 2 , W 2 , P 3 , W 3 , P 4 , and W 4 in the general formula (I) have the above-SO 2- Z as a substituent. , [3].
• Z 5 , Z 6 , Z 7 and Z 8 are independently substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, or substituted or unsubstituted heterocyclic groups, respectively. Represents. However, at least one of Z 5 , Z 6 , Z 7 and Z 8 has an ionic hydrophilic group as a substituent.
• Z 9 , Z 10 , Z 11 and Z 12 are independently substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, or substituted or unsubstituted heterocyclic groups, respectively. Represents. However, at least one of Z 9 , Z 10 , Z 11 and Z 12 has an ionic hydrophilic group as a substituent.
• R 31 , R 32 , R 33 , and R 34 are independently substituted or unsubstituted sulfamoyl groups, substituted or unsubstituted carbamoyl groups, and sulfo groups, respectively. , Or a carboxy group, and when a plurality of groups are present, they may be the same or different.
• o, p, q, and r each independently represent an integer of 1 to 4.
• the content of the dye represented by the general formula (I) is 3.0 to 5.0% by mass based on the total mass of the dye ink composition, and the dye ink composition is a cyan dye ink.
• the content of the compound represented by the general formula (II) is 0.5 to 2.0% by mass based on the total mass of the dye ink composition, and the dye ink composition is a cyan dye ink.
• a dye ink composition capable of forming an image having excellent printing density (particularly, color development on plain paper) and excellent ozone resistance and light resistance, a dye ink for inkjet recording, and a dye ink for inkjet recording.
• An inkjet recording method can be provided.
• the dye ink composition of the present invention is a dye ink composition containing a dye represented by the following general formula (I), water, and a compound represented by the following general formula (II).
• Q 1 , P 1 , W 1 , S 1 , Q 2 , P 2 , W 2 , S 2 , Q 3 , P 3 , W 3 , S 3 , Q 4 , P 4 , W 4 , and S 4 respectively.
• R 1 represents a hydrogen atom or a substituent.
• Ring A formed from Q 1 , P 1 , W 1 , and S 1 .
• Q 2, P 2, W 2 , and ring B formed from S 2 Ring C formed from Q 3 , P 3 , W 3 , and S 3 , and Q 4, P 4, W 4 , and ring D formed from S 4 represent each independently a substituted or unsubstituted benzene ring, or a 6-membered nitrogen-containing heterocyclic ring substituted or unsubstituted.
• the remaining one ring is a substituted or unsubstituted pyridine ring, substituted or unsubstituted.
• ring A a substituted or unsubstituted pyrimidine ring
• ring D a substituted or unsubstituted pyridazine ring
• the remaining two rings are independently substituted or unsubstituted pyridine rings, respectively.
• Substituted or unsubstituted pyrazine ring, substituted or unsubstituted pyrimidine ring, or substituted or unsubstituted pyridazine ring substituted or unsubstituted pyridazine ring.
• Ring A, Ring B, Ring C and Ring D if one ring represents a substituted or unsubstituted benzene ring, the remaining three rings are independently substituted or unsubstituted pyridine rings, respectively. , Substituted or unsubstituted pyrazine ring, substituted or unsubstituted pyrimidine ring, or substituted or unsubstituted pyridazine ring. Ring A, Ring B, Ring C and Ring D do not all represent simultaneously substituted or unsubstituted benzene rings.
• the dye represented by the general formula (I) has at least one ionic hydrophilic group as a substituent.
• 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 dye ink composition of the present invention can form an image having excellent printing density (particularly, color development on plain paper) and image durability (ozone resistance and light resistance) is complete. Although it has not been clarified in the above, the present inventors presume as follows.
• An image of cyan hue can be formed by an inkjet method using a dye ink composition containing a dye (water-soluble dye) represented by the general formula (I).
• a dye water-soluble dye represented by the general formula (I)
• the dye represented by the general formula (I) forms a relatively stable (metastable) phthalocyanine dye association state.
• the dye represented by the general formula (I) which has high water solubility in conjunction with the temperature and humidity of the surrounding environment when the dye ink composition is dried, is a dye that is more stable by using temperature and moisture as a driving force.
• the dye progresses to the associative state (change in existence state such as H-aggregate of dye: decrease in hue and color value at the same time), and as a result, the reflection density of the formed image decreases ( It is estimated that the print density will be low).
• an ink using a water-soluble phthalocyanine dye unlike an inkjet paper (having an image receiving layer supported on porous silica or alumina on a resin coated paper as a base paper), plain paper (the above image receiving layer is used).
• the dye ink composition permeates as it is in the thickness direction of the base paper when creating a printed matter on (not present), if the amount of the dye ink composition to be dropped is the same, the dye ink composition is dropped on the dedicated inkjet paper.
• the reflection density of the image obtained when the ink is dropped on plain paper is lower than that when the ink is dropped.
• the compound represented by the general formula (II) which is a compound having high flatness
• the dye represented by the general formula (I) suppresses the fading of the cyan hue of the image without causing a chemical change. It is considered that the image durability (particularly ozone resistance and light resistance) could be improved.
• the substituent group A includes the following substituents.
• halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• alkyl group examples include linear or branched substituted or unsubstituted alkyl groups.
• Alkyl groups among the substituents described below also represent alkyl groups of such a concept.
• alkyl group preferably, an alkyl group having 1 to 30 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a t-butyl group, an n-octyl group, an eicosyl group, 2- Examples thereof include a chloroethyl group, a 2-cyanoethyl group, and a 2-ethylhexyl group.
• cycloalkyl group examples include a substituted or unsubstituted cycloalkyl group, preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, for example, a cyclohexyl group, a cyclopentyl group, a 4-n-dodecylcyclohexyl.
• examples thereof include groups, and the bicycloalkyl group is preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms.
• Groups include, for example, a bicyclo [1,2,2] heptane-2-yl group, a bicyclo [2,2,2] octane-3-yl group and the like.
• aralkyl group examples include a substituted or unsubstituted aralkyl group, and the substituted or unsubstituted aralkyl group is preferably an aralkyl group having 7 to 30 carbon atoms.
• a benzyl group and a 2-phenethyl group can be mentioned.
• alkenyl group examples include linear, branched, cyclically substituted or unsubstituted alkenyl groups, and include cycloalkenyl groups and bicycloalkenyl groups.
• the alkenyl group preferably includes a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, for example, a vinyl group, an allyl group, a prenyl group, a geranyl group, an oleyl group and the like, and the cycloalkenyl group is preferable.
• Is a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms that is, a monovalent group from which one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms has been removed, for example, a 2-cyclopentene-1-yl group.
• Examples thereof include 2-cyclohexene-1-yl group
• examples of the bicycloalkenyl group include a substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a double bond.
• a monovalent group from which one hydrogen atom of a bicycloalkene having one is removed for example, a bicyclo [2,2,1] hept-2-ene-1-yl group, a bicyclo [2,2,2] octo-2- Examples thereof include an en-4-yl group.
• the alkynyl group preferably includes a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, for example, an ethynyl group, a propargyl group, a trimethylsilylethynyl group and the like.
• the aryl group is preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, for example, a phenyl group, a p-tolyl group, a naphthyl group, an m-chlorophenyl group, an o-hexadecanoylaminophenyl group and the like. Can be mentioned.
• the heterocyclic group is preferably a monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, and more preferably the number of carbon atoms.
• Examples include 3 to 30 5- or 6-membered aromatic heterocyclic groups such as 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group and the like.
• non-aromatic heterocyclic groups include morpholinyl groups and the like.
• the alkyloxy group is preferably a substituted or unsubstituted alkyloxy group having 1 to 30 carbon atoms, for example, a methoxy group, an ethoxy group, an isopropoxy group, a t-butoxy group, an n-octyloxy group, or 2-methoxy. Examples include an ethoxy group.
• the aryloxy group is preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, for example, a phenoxy group, a 2-methylphenoxy group, a 4-t-butylphenoxy group, a 3-nitrophenoxy group, 2 -Tetradecanoylaminophenoxy group and the like can be mentioned.
• the silyloxy group is preferably a substituted or unsubstituted silyloxy group having 0 to 20 carbon atoms, for example, a trimethylsilyloxy group, a diphenylmethylsilyloxy group and the like.
• the heterocyclic oxy group preferably includes a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, for example, 1-phenyltetrazole-5-oxy group, 2-tetrahydropyranyloxy group and the like.
• the acyloxy group is preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, for example, an acetyloxy group.
• Pivaloyloxy group, stearoyloxy group, benzoyloxy group, p-methoxyphenylcarbonyloxy group and the like can be mentioned.
• the carbamoyloxy group is preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, for example, N, N-dimethylcarbamoyloxy group, N, N-diethylcarbamoyloxy group, morpholinocarbonyloxy group, N. , N-di-n-octylaminocarbonyloxy group, Nn-octylcarbamoyloxy group and the like.
• the alkyloxycarbonyloxy group is preferably a substituted or unsubstituted alkyloxycarbonyloxy group having 2 to 30 carbon atoms, for example, a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a t-butoxycarbonyloxy group, an n-octyloxy group. Examples thereof include a carbonyloxy group.
• the aryloxycarbonyloxy group is preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, for example, a phenoxycarbonyloxy group, a p-methoxyphenoxycarbonyloxy group, pn-hexadecyloxy. Examples thereof include a phenoxycarbonyloxy group.
• the amino group includes an alkylamino group, an arylamino group, and a heterocyclic amino group, preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, and a substituted or absence of 6 to 30 carbon atoms.
• Substituted anilino groups such as methylamino group, dimethylamino group, anilino group, N-methyl-anilino group, diphenylamino group, triazinylamino group and the like can be mentioned.
• the acylamino group is preferably a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, for example, an acetylamino group.
• Examples thereof include a pivaloylamino group, a lauroylamino group, a benzoylamino group, a 3,4,5-tri-n-octyloxyphenylcarbonylamino group and the like.
• the aminocarbonylamino group is preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, for example, a carbamoylamino group, an N, N-dimethylaminocarbonylamino group, an N, N-diethylaminocarbonylamino group. , Morphorinocarbonylamino group and the like.
• the alkyloxycarbonylamino group is preferably a substituted or unsubstituted alkyloxycarbonylamino group having 2 to 30 carbon atoms, for example, a methoxycarbonylamino group, an ethoxycarbonylamino group, a t-butoxycarbonylamino group, an n-octadecyloxy. Examples thereof include a carbonylamino group and an N-methyl-methoxycarbonylamino group.
• the aryloxycarbonylamino group is preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, for example, a phenoxycarbonylamino group, a p-chlorophenoxycarbonylamino group, or an mn-octyloxyphenoxy. Examples thereof include a carbonylamino group.
• the sulfamoylamino group is preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, for example, a sulfamoylamino group, an N, N-dimethylaminosulfonylamino group, Nn-. Examples thereof include an octylaminosulfonylamino group.
• the alkyl or arylsulfonylamino group is preferably a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, for example, a methylsulfonylamino group.
• the heterocyclic sulfonylamino group preferably includes a substituted or unsubstituted heterocyclic sulfonylamino group having 1 to 12 carbon atoms, for example, a 2-thiophenesulfonylamino group and a 3-pyridinesulfonylamino group.
• the alkylthio group preferably includes a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, for example, a methylthio group, an ethylthio group, an n-hexadecylthio group and the like.
• the arylthio group preferably includes a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, for example, a phenylthio group, a p-chlorophenylthio group, an m-methoxyphenylthio group and the like.
• heterocyclic thio group examples include a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, for example, a 2-benzothiazolylthio group, a 1-phenyltetrazole-5-ylthio group and the like.
• the sulfamoyl group is preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, for example, an N-ethylsulfamoyl group, an N- (3-dodecyloxypropyl) sulfamoyl group, N, N-dimethylsul.
• Examples thereof include a famoyl group, an N-acetylsulfamoyl group, an N-benzoyl sulfamoyl group, an N- (N'-phenylcarbamoyl) sulfamoyl group and the like.
• the alkyl or arylsulfinyl group is preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, for example, a methylsulfinyl group or an ethylsulfinyl group. , Penylsulfinyl group, p-methylphenylsulfinyl group and the like.
• the heterocyclic sulfinyl group is preferably a substituted or unsubstituted heterocyclic sulfoxide group having 1 to 20 carbon atoms, and examples of the heterocyclic sulfinyl group include a 4-pyridinesulfinyl group.
• the alkyl or arylsulfonyl group is preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, for example, a methylsulfonyl group or an ethylsulfonyl group. , Phenylsulfonyl group, p-methylphenylsulfonyl group and the like.
• the heterocyclic sulfonyl group preferably includes a substituted or unsubstituted heterocyclic sulfonyl group having 1 to 20 carbon atoms, for example, a 2-thiophene sulfonyl group and a 3-pyridine sulfonyl group.
• acyl group preferably, a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, a substituted or no substituted group having 2 to 30 carbon atoms is preferable.
• Heterocyclic carbonyl group bonded to a carbonyl group at the substituted carbon atom such as acetyl group, pivaloyl group, 2-chloroacetyl group, stearoyl group, benzoyl group, pn-octyloxyphenylcarbonyl group, 2-pyridyl Examples thereof include a carbonyl group and a 2-furylcarbonyl group.
• the aryloxycarbonyl group is preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, for example, a phenoxycarbonyl group, an o-chlorophenoxycarbonyl group, an m-nitrophenoxycarbonyl group, pt-. Examples thereof include a butylphenoxycarbonyl group.
• alkoxycarbonyl group examples include a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, a t-butoxycarbonyl group, and an n-octadecyloxycarbonyl group.
• the heterocyclic oxycarbonyl group is preferably a heterocyclic oxycarbonyl group having 2 to 20 carbon atoms, and examples of the heterocyclic oxycarbonyl group include a 2-pyridyloxycarbonyl group.
• the carbamoyl group is preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms, for example, a carbamoyl group, an N-methylcarbamoyl group, an N, N-dimethylcarbamoyl group, an N, N-di-n-octyl. Examples thereof include a carbamoyl group and an N- (methylsulfonyl) carbamoyl group.
• the aryl or heterocyclic azo group is preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms, for example, a phenylazo group or p-chlorophenylazo.
• Groups, 5-ethylthio-1,3,4-thiadiazole-2-ylazo group and the like can be mentioned.
• the imide group preferably includes an N-succinimide group, an N-phthalimide group and the like.
• the phosphino group preferably includes a substituted or unsubstituted phosphino group having 0 to 30 carbon atoms, for example, a dimethylphosphino group, a diphenylphosphino group, a methylphenoxyphosphino group and the like.
• the phosphinyl group preferably includes a substituted or unsubstituted phosphinyl group having 0 to 30 carbon atoms, for example, a phosphinyl group, a dioctyloxyphosphinyl group, a diethoxyphosphinyl group and the like.
• the phosphinyloxy group preferably includes a substituted or unsubstituted phosphinyloxy group having 0 to 30 carbon atoms, for example, a diphenoxyphosphinyloxy group, a dioctyloxyphosphinyloxy group and the like.
• the phosphinylamino group is preferably a substituted or unsubstituted phosphinylamino group having 0 to 30 carbon atoms, for example, a dimethoxyphosphinylamino group or a dimethylaminophosphinylamino group.
• the silyl group preferably includes a substituted or unsubstituted silyl group having 0 to 30 carbon atoms, for example, a trimethylsilyl group, a t-butyldimethylsilyl group, a phenyldimethylsilyl group and the like.
• Examples of the ionic hydrophilic group include a sulfo group (-SO 3 M), a carboxy group (-COOM), a thiocarboxy group, a sulfino group (-SO 2 M), a phosphono group (-PO (OR) (OM), and a dihydroxy).
• the M represents a hydrogen atom or a countercation.
• the R represents a monovalent substituent (eg, an alkyl group, an aryl). Groups) and the like are included. Among them, a sulfo group (-SO 3 M), a carboxy group (-COOM) and a phosphate group (-PO (OM) 2 ) are preferable, and a sulfo group (-SO 3 M), in particular, And a carboxy group (-COMM) are preferred.
• the ionic hydrophilic group may be in the salt state, and examples of counter cations forming the salt include ammonium ion, alkali metal ion (eg, lithium ion, sodium ion, potassium ion) and organic. Cations (eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium ion) are included.
• M is preferably a hydrogen atom, an ammonium ion or an alkali metal 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, and among them, lithium ion is most preferable.
• the salt when the compound is a salt, the salt is dissolved in ions in a completely dissociated state and exists in the water-soluble ink.
• it has an ionic hydrophilic group having a high acid dissociation constant (pKa), most of it may be dissociated and partially dissolved in a salt state.
• Q 1 , P 1 , W 1 , S 1 , Q 2 , P 2 , W 2 , S 2 , Q 3 , P 3 , W 3 , S 3 , Q 4 , P 4 , W 4 , and S 4 respectively.
• R 1 represents a hydrogen atom or a substituent.
• Ring A formed from Q 1 , P 1 , W 1 , and S 1 .
• Q 2, P 2, W 2 , and ring B formed from S 2 Ring C formed from Q 3 , P 3 , W 3 , and S 3 , and Q 4, P 4, W 4 , and ring D formed from S 4 represent each independently a substituted or unsubstituted benzene ring, or a 6-membered nitrogen-containing heterocyclic ring substituted or unsubstituted.
• the remaining one ring is a substituted or unsubstituted pyridine ring, substituted or unsubstituted.
• ring A a substituted or unsubstituted pyrimidine ring
• ring D a substituted or unsubstituted pyridazine ring
• the remaining two rings are independently substituted or unsubstituted pyridine rings, respectively.
• Substituted or unsubstituted pyrazine ring, substituted or unsubstituted pyrimidine ring, or substituted or unsubstituted pyridazine ring substituted or unsubstituted pyridazine ring.
• Ring A, Ring B, Ring C and Ring D if one ring represents a substituted or unsubstituted benzene ring, the remaining three rings are independently substituted or unsubstituted pyridine rings, respectively. , Substituted or unsubstituted pyrazine ring, substituted or unsubstituted pyrimidine ring, or substituted or unsubstituted pyridazine ring. Ring A, Ring B, Ring C and Ring D do not all represent simultaneously substituted or unsubstituted benzene rings.
• the dye represented by the general formula (I) has at least one ionic hydrophilic group as a substituent.
• preferred substituents include chemically bondable substituents selected from the substituent group A. ..
• the dye represented by the general formula (I) has at least one ionic hydrophilic group as a substituent. "Having an ionic hydrophilic group as a substituent” means having a substituent containing an ionic hydrophilic group, and at least an ionic hydrophilic group is substituted with a group other than the ionic hydrophilic group. This includes the case where the group is provided as a substituent.
• At least one is a group selected from -SO 2- Z, -SO 3 M, and -CO 2 M. It is preferable to have at least one.
• M represents a hydrogen atom or a counter cation.
• Z represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.
• At least one ring of ring A, ring B, ring C and ring D has one or more substituents selected from -SO 2- Z and -SO 3 M, and more preferably -SO 2-. It is particularly preferable to have Z.
• At least one ring of ring A, ring B, ring C and ring D has at least one group selected from -SO 2- Z, -SO 3 M, and -CO 2 M, and is substituted. It may have a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom) as a group.
• a halogen atom for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom
• Dye represented by the general formula (I) the preferably has three to -SO 2 -Z from 1, P 1 in the general formula (I), W 1, P 2, W 2, P It is more preferable that 1 to 3 of 3 , W 3 , P 4 , and W 4 have -SO 2- Z as a substituent (R 1 represents -SO 2- Z). Ring having -SO 2 -Z as a substituent, is preferably a benzene ring.
• Z is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group (specific examples of the heterocyclic group are the same as the heterocyclic group in the above-mentioned substituent group A). Things can be mentioned.)
• it represents an alkyl group having a total carbon number of 1 to 20 substituted or unsubstituted, or an aryl group having a total carbon number of 6 to 20 substituted or unsubstituted.
• Z preferably has a substituent containing an ionic hydrophilic group.
• the ionic hydrophilic group is preferably an acidic group, more preferably a sulfo group, a carboxy group or a phosphoric acid group, and even more preferably a sulfo group or a carboxy group.
• Z is preferably an alkyl group, an aryl group or a heterocyclic group having a substituent containing at least an ionic hydrophilic group.
• the "alkyl group, aryl group or heterocyclic group having at least a substituent containing an ionic hydrophilic group” is "an alkyl group, an aryl group or a heterocyclic group having at least an ionic hydrophilic group as a substituent".
• Z is more preferably an alkyl group having a total carbon number of 1 to 20 substituted with an ionic hydrophilic group or an aryl group having a total carbon number of 6 to 20 substituted with an ionic hydrophilic group, and is ionic hydrophilic.
• Alkyl groups having a total carbon number of 1 to 5 substituted with a sex group or aryl groups having a total carbon number of 6 to 12 substituted with an ionic hydrophilic group are more preferable, and total carbon substituted with a sulfo group or a carboxy group.
• Alkyl groups of numbers 1 to 3 or aryl groups with a total carbon number of 6 to 10 substituted with a sulfo group or a carboxy group are particularly preferable.
• Z is an alkyl group, an aryl group or a heterocyclic group having a group in which at least an ionic hydrophilic group is substituted with a group other than the ionic hydrophilic group as a substituent, other than the above ionic hydrophilic group.
• the group thereof include a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted sulfamoyl group, a substituted or unsubstituted carbamoyl group, and a substituent.
• an unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group and the like can be mentioned.
• substituents can further have one or more substituents, as the further substituent, for example, a group having a substituent selected from the above-mentioned Substituent Group A is also the above-mentioned ionic hydrophilic group. Included in examples of groups other than.
• the carbon number of the group other than the ionic hydrophilic group is preferably 1 to 20, and more preferably 1 to 10.
• Z may have a substituent other than the substituent containing the ionic hydrophilic group in addition to the substituent containing the ionic hydrophilic group.
• substituent other than the substituent containing the ionic hydrophilic group include a halogen atom, a hydroxy group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and the like.
• substituents can further have one or more substituents
• the group having a substituent selected from the above-mentioned substituents as a further substituent also contains the above-mentioned ionic hydrophilic group.
• substituents other than groups are included in the examples of substituents other than groups.
• substituent other than the substituent containing the ionic hydrophilic group is an organic group (a group containing at least one carbon atom), it is preferably an organic group having 1 to 10 carbon atoms, and 1 to 10 carbon atoms. More preferably, it is an organic group of 6.
• lithium ion, sodium ion, potassium ion, ammonium ion preferably, lithium ions, sodium ions, more preferably potassium ions, lithium ions, sodium ions, Most preferable from the viewpoint of water solubility of dye, storage stability of ink, and image quality of inkjet printed matter.
• lithium ion, sodium ion, potassium ion, ammonium ion preferably a sodium ion, a potassium ion, more preferably an ammonium ion, sodium ion, potassium ion, water-soluble dyes, the storage stability of the ink Most preferable from the viewpoint of property and image quality of the inkjet printed matter.
• ring A, ring B, ring C, or ring D represents a 6-membered nitrogen-containing heterocycle, they independently represent a pyridine ring, a pyrazine ring, a pyrimidine ring, or a pyridazine ring. It is preferably a pyridine ring, a pyrazine ring, or a pyrimidine ring, more preferably a pyridine ring or a pyrazine ring, further preferably a 3-pyridine ring or a 4-pyridine ring, and particularly a 3-pyridine ring (Q).
• the dye represented by the general formula (I) is a dye represented by the following general formula (III) is from the viewpoint of achieving both image fastness and water solubility (long-term storage stability of water-soluble ink). Is preferable.
• Q 1 , P 1 , W 1 , S 1 , Q 2 , P 2 , W 2 , S 2 , Q 3 , P 3 , W 3 , S 3 , Q 4 , P 4 , W 4 , and S 4 respectively.
• R 1 represents a hydrogen atom or a substituent.
• Ring A formed from Q 1 , P 1 , W 1 , and S 1 .
• Q 2, P 2, W 2 , and ring B formed from S 2 Ring C formed from Q 3 , P 3 , W 3 , and S 3 , and Q 4, P 4, W 4 , and ring D formed from S 4 represent each independently a substituted or unsubstituted benzene ring, or a 6-membered nitrogen-containing heterocyclic ring substituted or unsubstituted.
• the remaining one ring is a substituted or unsubstituted pyridine ring, substituted or unsubstituted.
• ring A a substituted or unsubstituted pyrimidine ring
• ring D a substituted or unsubstituted pyridazine ring
• the remaining two rings are independently substituted or unsubstituted pyridine rings, respectively.
• Substituted or unsubstituted pyrazine ring, substituted or unsubstituted pyrimidine ring, or substituted or unsubstituted pyridazine ring substituted or unsubstituted pyridazine ring.
• Ring A, Ring B, Ring C and Ring D if one ring represents a substituted or unsubstituted benzene ring, the remaining three rings are independently substituted or unsubstituted pyridine rings, respectively. , Substituted or unsubstituted pyrazine ring, substituted or unsubstituted pyrimidine ring, or substituted or unsubstituted pyridazine ring. Ring A, Ring B, Ring C and Ring D do not all represent simultaneously substituted or unsubstituted benzene rings.
• the dye represented by the general formula (I) has -SO 2- Z 1 as a substituent, and Z 1 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted. It represents an unsubstituted heterocyclic group, and x represents 1 to 3.
• Z 1 is may be different from each in the presence of two or more may be the same. At least one Z 1 has an ionic hydrophilic group as a substituent.
• the ring A, the ring B, the ring C and the ring D are synonymous with the ring A, the ring B, the ring C and the ring D in the general formula (I), and the preferred examples are also the same.
• a preferred example of Z 1 is the same as Z described above.
• the substitution position of -SO 2- Z 1 is the ⁇ -position or the ⁇ -position (replace with the ⁇ -position hydrogen atom or the ⁇ -position hydrogen atom).
• at least one -SO 2- Z 1 substitution position is at the ⁇ -position, and all -SO 2- Z 1 substitutions at the ⁇ -position are image fastness linked to dye association. Most preferable from the viewpoint of (particularly ozone gas resistance).
• the ⁇ -position and ⁇ -position of the phthalocyanine skeleton are as shown in the following formula (a).
• Het represents a nitrogen-containing 6-membered heterocycle.
• each Z 1 may be the same or different, but the dyes must all be the same. It is preferable from the viewpoint of image fastness (ozone gas resistance) linked to the association of dyes.
• M when the ionic hydrophilic group represents -SO 3 M or -CO 2 M is a specific example of M in the above general formula (I) and It is synonymous with the preferred range and the preferred examples are the same.
• Z 1 may have other substituents in addition to the ionic hydrophilic group, and examples of the other substituents include substituents selected from the above-mentioned Substituent Group A.
• Preferred substituents are a halogen atom, a hydroxyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted sulfamoyl group, an alkyl or arylsulfonyl group.
• Substituted or unsubstituted carbamoyl group more preferably hydroxyl group, substituted or unsubstituted amino group, substituted or unsubstituted sulfamoyl group, alkyl or arylsulfonyl group, substituted or unsubstituted carbamoyl group, and further. It is preferably a substituted or unsubstituted sulfamoyl group, a substituted or unsubstituted carbamoyl group, and particularly preferably a substituted or unsubstituted sulfamoyl group.
• Preferred examples of -SO 2- Z 1 are -SO 2 (CH 2 ) 3- SO 3 M, -SO 2 (CH 2 ) 4- SO 3 M, -SO 2 (CH 2 ) 5- SO 3 M. , -SO 2 (CH 2 ) 3- CO 2 M, -SO 2 (CH 2 ) 4- CO 2 M, -SO 2 (CH 2 ) 5- CO 2 M, -SO 2 C 2 H 4 OC 2 H 4 SO 3 M, -SO 2 CH 2 CH (OH) CH 2 SO 3 M, -SO 2 CH 2 CH (OH) CH 2 CO 2 M, -SO 2 (CH 2 ) 2 CH (CH 3 ) SO 3 M, -SO 2 (CH 2 ) 3 CH (CH 3 ) SO 3 M, -SO 2 (CH 2 ) 3- SO 2 NHCH 2 CH (OH) CH 2 SO 3 M, -SO 2 (CH 2 ) 3 -SO 2 NHCH 2 CH (OH) CH 2 CO 2 M, -SO 2 (CH 2 ) 3 -SO 2
• M represents a hydrogen atom or a counter cation.
• the counter cation is not particularly limited, and examples thereof include alkali metal ion, ammonium ion, and organic cation (tetramethylammonium, guanidinium, pyridinium, etc.).
• M is preferably a hydrogen atom, an ammonium ion or an alkali metal 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, and lithium ions are most preferable.
• a lithium salt of a sulfo group (-SO 3 Li) is preferable because it enhances the solubility of the dye and improves the ink stability.
• M may be a divalent counter cation.
• M be a divalent counter cation is, 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.
• M represents a specific cation (for example, lithium ion)
• the counter cation having substantially the highest abundance ratio is lithium ion.
• It can contain a class phosphonium ion, a sulfonium ion, and the like.
• the amount of lithium ions is preferably 50% or more, more preferably 60% or more, still more preferably 80% or more, particularly preferably 90% or more, based on the total amount of M, which is the upper limit. Is preferably 100%.
• the dye represented by the general formula (I) (partial azaphthalocyanine dye) can be synthesized by a known method (for example, the method described in Examples of Japanese Patent No. 4516744).
• the type of dye represented by the general formula (I) contained in the dye ink composition of the present invention may be only one type, may be two or more types, but is preferably two or more types.
• the dye ink composition of the present invention can be used as a dye represented by the general formula (I).
• a dye in which three of the four rings of ring A, ring B, ring C and ring D are 6-membered nitrogen-containing heterocycles preferably dyes represented by the following general formula (I-1)).
• Dyes in which two of the four rings of ring A, ring B, ring C and ring D are 6-membered nitrogen-containing heterocycles preferably dyes represented by the following general formula (I-2-1) and the following general formulas.
• At least one of the dyes represented by (I-2-2)), and It may contain a dye in which one of the four rings of ring A, ring B, ring C and ring D is a 6-membered nitrogen-containing heterocycle (preferably a dye represented by the following general formula (I-3)). preferable.
• Het independently represents a pyridine ring, a pyrazine ring, a pyrimidine ring, or a pyridazine ring, respectively.
• R 11 represents a substituent.
• r1 represents 1 to 4. If R 11 there are a plurality, a plurality of R 11 may be the same or different.
• the dye represented by the general formula (I-1) has at least one ionic hydrophilic group as a substituent.
• Het independently represents a pyridine ring, a pyrazine ring, a pyrimidine ring, or a pyridazine ring, respectively.
• R 21 and R 22 each independently represent a substituent.
• r21 and r22 independently represent 0 to 4, respectively. If R 21 there are a plurality, the plurality of R 21 may be the same or different. If R 22 there are a plurality, a plurality of R 22 may be the same or different.
• the dye represented by the general formula (I-2-1) has at least one ionic hydrophilic group as a substituent.
• Het independently represents a pyridine ring, a pyrazine ring, a pyrimidine ring, or a pyridazine ring, respectively.
• R 23 and R 24 each independently represent a substituent.
• r23 and r24 independently represent 0 to 4, respectively. If R 23 there are a plurality, a plurality of R 23 may be the same or different. If R 24 there are a plurality, a plurality of R 24 may be the same or different.
• the dye represented by the general formula (I-2-2) has at least one ionic hydrophilic group as a substituent.
• Het represents a pyridine ring, a pyrazine ring, a pyrimidine ring, or a pyridazine ring.
• R 31 , R 32 and R 33 each independently represent a substituent.
• r31, r32 and r33 independently represent 0 to 4, respectively. If R 31 there are a plurality, a plurality of R 31 may be the same or different. If R 32 there are a plurality, a plurality of R 32 may be the same or different. If R 33 there are a plurality, a plurality of R 33 may be the same or different.
• the dye represented by the general formula (I-3) has at least one ionic hydrophilic group as a substituent.
• R 11 in the general formula (I-1) are the same as those described as the substituents that the rings A, B, C and D may have. Further, r1 representing the number of substituents preferably represents 1 to 3.
• R 21 and R 22 in the general formula (I-2-1) are the same as those described as the substituents that the rings A, B, C and D may have. is there. Further, r21 and r22 representing the number of substituents preferably represent 1 to 3, respectively.
• R 23 and R 24 in the general formula (I-2-2) are the same as those described as the substituents that the rings A, B, C and D may have. is there. Further, r23 and r24 representing the number of substituents preferably represent 1 to 3, respectively.
• R 31 , R 32 and R 33 in the general formula (I-3) are the same as those described as the substituents that the rings A, B, C and D may have. Is. Further, r31, r32 and r33 representing the number of substituents preferably represent 1 to 3, respectively.
• the dye ink composition of the present invention contains 4 to 30% by mass of the dye represented by the general formula (I-1) with respect to the total mass of the dye represented by the general formula (I). A total of 15 to 45% by mass of at least one of the dye represented by I-2-1) and the dye represented by the general formula (I-2-2) is contained, and the dye represented by the general formula (I-3) is represented. It is preferable to contain 20 to 50% by mass of the dye to be used.
• the dye represented by the general formula (I) or (III) will be given below, but the present invention is not limited thereto.
• the substituted sulfonyl group (-SO 2 Z) is substituted with any hydrogen atom at the ⁇ -position, and is not substituted with the portion described by "H" in each structural formula. Represents.
• the substitution position is distinguished by a specific example in which two rings represent a substituted benzene ring and the remaining two rings are heterocycles. I will list it without mentioning it. That is, the following specific examples include positional isomers having different substitution positions as described below (E1-7) to (E1-8) or the following (E1-9) to (E1-10), respectively. Is. R represents a substituent.
• the dye ink composition of the present invention may further contain a compound (color toning agent) represented by the following general formula (Cy-1) in addition to the dye represented by the general formula (I).
• a compound (color toning agent) represented by the following general formula (Cy-1) in addition to the dye represented by the general formula (I).
• Z 5 , Z 6 , Z 7 and Z 8 are independently substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, or substituted or unsubstituted heterocyclic groups, respectively. Represents. However, at least one of Z 5 , Z 6 , Z 7 and Z 8 has an ionic hydrophilic group as a substituent.
• the alkyl group, aryl group, and heterocyclic group represented by Z 5 , Z 6 , Z 7 , and Z 8 in the general formula (Cy-1) are each preferable substituents of the general formula (I). Similar to the alkyl, aryl, and heterocyclic groups described as Z in SO 2- Z, with preferred examples as well.
• the compound represented by the general formula (Cy-1) has a substituted sulfonyl group (-SO 2- Z 5 , -SO 2- Z 6 , -SO 2- Z 7 , and -SO 2- Z 8 ) at the ⁇ -position. It is a substituted phthalocyanine dye. That is, in the general formula (Cy-1), -SO 2- Z 5 , -SO 2- Z 6 , -SO 2- Z 7 and -SO 2- Z 8 are replaced with hydrogen atoms at the ⁇ -position. It is not replaced with a hydrogen atom at the ⁇ -position.
• the compound represented by the general formula (Cy-1) can be synthesized by a known method (for example, the methods described in Japanese Patent No. 39949385, No. 4512543 and No. 4854250).
• the ⁇ -position and ⁇ -position of the phthalocyanine skeleton are as shown in the following formula (b).
• the dye ink composition of the present invention may further contain a compound (color toning agent) represented by the following general formula (Cy-2) in addition to the dye represented by the general formula (I).
• a compound (color toning agent) represented by the following general formula (Cy-2) in addition to the dye represented by the general formula (I).
• Z 9 , Z 10 , Z 11 and Z 12 are independently substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, or substituted or unsubstituted heterocyclic groups, respectively. Represents. However, at least one of Z 9 , Z 10 , Z 11 and Z 12 has an ionic hydrophilic group as a substituent.
• the alkyl group, aryl group, and heterocyclic group represented by Z 9 , Z 10 , Z 11 , and Z 12 in the general formula (Cy-2) are each preferable substituents of the general formula (I). Similar to the alkyl, aryl, and heterocyclic groups described as Z in SO 2- Z, with preferred examples as well.
• the compound represented by the general formula (Cy-2) has a substituted sulfonyl group (-SO 2- Z 9 , -SO 2- Z 10 , -SO 2- Z 11 , and -SO 2- Z 12 ) at the ⁇ -position. It is a substituted phthalocyanine dye. That is, in the general formula (Cy-2), -SO 2- Z 9 , -SO 2- Z 10 , -SO 2- Z 11 , and -SO 2- Z 12 are replaced with hydrogen atoms at the ⁇ -position. It is not replaced with a hydrogen atom at the ⁇ -position.
• the compound represented by the general formula (Cy-2) can be synthesized by a known method (for example, the method described in Japanese Patent No. 39949385 and No. 4854250).
• the ⁇ -position and ⁇ -position of the phthalocyanine skeleton are as shown in the above formula (b).
• the ⁇ -position substitution between molecules rather than intramolecularly And ⁇ -position substitution ratio can be adjusted, and as a result, it is possible to achieve both high printing density (on plain paper and on special paper for inkjet) and good image durability at a high level.
• R 31 , R 32 , R 33 , and R 34 are independently substituted or unsubstituted sulfamoyl groups, substituted or unsubstituted carbamoyl groups, and sulfo groups, respectively.
• a carboxy group and when a plurality of groups are present, they may be the same or different.
• o, p, q, and r each independently represent an integer of 1 to 4.
• the toning agent represented by any of the general formulas (Cy-3) to (Cy-6) has a substituent introduction position with respect to the ⁇ -position and ⁇ -position shown in the above formula (a) of the phthalocyanine dye skeleton. It is an ⁇ -position / ⁇ -position substitution mixture (for example, ⁇ -position / ⁇ -position ⁇ 10% / 90% to 50% / 50%) having no selectivity for.
• the preferred R 31 , R 32 , R 33 , and R 34 are independently substituted or absent from the viewpoint of availability of raw materials and ease of synthesis.
• Substituted sulfamoyl groups, carbamoyl groups, sulfo groups (-SO 3 M) and carboxy groups (-COOM) can be mentioned.
• the substituted sulfamoyl group (-SO 2 NR 41 R 42 ) is based on the achievement level of the required performance of inkjet.
• R 41 and R 42 independently represent a hydrogen atom or a substituent), an unsubstituted sulfamoyl group (-SO 2 NH 2 ), and a sulfo group (-SO 3 M) are preferable, and among them, a substituted sulfamoyl group (-SO 3 M) is preferable.
• the counter cation (M) of the ionic hydrophilic group contained in the toning agent represented by any of the above general formulas (Cy-3) to (Cy-6) represents a hydrogen atom or a counter cation.
• the counter cation is not particularly limited, and examples thereof include alkali metal ion, ammonium ion, and organic cation (tetramethylammonium, guanidinium, pyridinium, etc.).
• M is preferably a hydrogen atom, an ammonium ion or an alkali metal 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, and lithium ions are most preferable. In particular, a lithium salt of a sulfo group (-SO 3 Li) is preferable because it enhances the solubility of the dye and improves the ink stability.
• M represents lithium ion, not all M need to be lithium ion, but it is preferable that the counter cation having substantially the highest abundance ratio is lithium ion.
• hydrogen atom under the condition of such abundance ratio, hydrogen atom, alkali metal ion (for example, sodium ion, potassium ion), alkaline earth metal ion (for example, magnesium ion, calcium ion, etc.), quaternary ammonium ion, 4 It can contain a class phosphonium ion, a sulfonium ion and the like.
• the amount of lithium ions is preferably 50% or more, more preferably 60% or more, still more preferably 80% or more, particularly preferably 90% or more, based on the total amount of M, which is the upper limit. Is preferably 100%.
• O, p, q, and r each independently represent an integer of 1 to 4, but 1 to 3 is more preferable, 1 to 2 is particularly preferable, and 1 is the most preferable. Further, a mixture of the general formulas (Cy-3), (Cy-4), (Cy-5) and (Cy-6) is preferable from the viewpoint of dye availability as a colorant. As a specific compound example, C.I. I. Direct blue 86, 87, 199 can be mentioned.
• the phthalocyanine derivative represented by any of the general formulas (Cy-3) to (Cy-6) that can be used in the present invention is, for example, "Parthalocyanine-Chemistry and Function-" by Shirai-Kobayashi, co-authored by IPC Co., Ltd. (P.1-62), C.I. C. Leznoff-A. B. P. It can also be synthesized by describing or quoting or combining methods similar to those described and quoted in'Physalocynines-Properties and Applications'(P.1-54) co-authored by Lever and published by VCH.
• a colorant other than the dye represented by the general formula (I) and other than the compound described above can also be contained as a combined dye. Typical dyes are shown below.
• "CI” is an abbreviation for "color index”. ⁇ C. I. Direct Blue: 6, 22, 25, 71, 78, 90, 106, 189, 262, 264, 276, 282, 314, etc. I.
• Acid Blue 9, 22, 40, 59, 93, 102, 104, 113, 117, 120, 167, 185, 197, 224, 228, 229, 234, 242, 243, 249, 254, 275, 279, 283 , 310, 357 and the like. Further, the compound described in International Publication No. 2007/091631 or JP-A-2005-179469 may be included.
• Dye ink composition general formulas content T 1 of the weight of the dye represented by the formula (I), the content T 2 and the general mass of the dye represented by the general formula (Cy-1)
• the ratio to T 4 (T 1 / T 2 / T 3 / T 4 ) is 45 to 100/0 to 35/0 to 10 from the viewpoint of achieving both the print density of plain paper and the image fastness on inkjet paper.
• T 1 / T 2 / T 3 / T 4 the long-term stability of the ink over time (change in viscosity, change in surface tension, suppression of precipitates, etc.) is excellent, and the printing sample using the ink High level of required performance of excellent photographic density (color development on inkjet paper and plain paper), suppression of bronze gloss of photographic sample, and image durability of photographic sample (especially ozone resistance and light resistance on inkjet dye) You can get a satisfactory effect with.
• the dye ink composition of the present invention is preferably for cyan dye ink.
• the content (% by mass) of the dye represented by the general formula (I) in the dye ink composition of the present invention is based on the total mass of the dye ink composition. It is preferably 1.0% by mass or more and 8.0% by mass or less, more preferably 2.0% by mass or more and 6.0% by mass or less, and 3.0% by mass or more and 5.5% by mass or less. The following is more preferable, and among them, 3.0% by mass or more and 5.0% by mass or less is most preferable from the viewpoint of print density and ink ejection reliability.
• the dye ink composition of the present invention in addition to the compound represented by the general formula (I), the compounds represented by the general formulas (Cy-1) to (Cy-6), other phthalocyanine dyes or the above.
• a partial azaphthalocyanine dye other than the general formula (I) or a triarylmethane dye is used in combination as a colorant, all the dyes in the dye ink composition (preferably the dye ink composition for cyan dye ink)
• the total content (% by mass) is preferably 1.0% by mass or more and 8.0% by mass or less, and 2.0% by mass or more and 6.0% by mass or less, based on the total mass of the dye ink composition. More preferably, it is more preferably 3.0% by mass or more and 5.5% by mass or less, and more preferably 3.0% by mass or more and 5.0% by mass or less is the printing density and ink ejection reliability. Most preferable from the viewpoint of sex.
• 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.
• the compound represented by the general formula (II) has at least one hydrophilic group in one molecule.
• hydrophilic groups are the I / O calculated values of ⁇ 0: organic value ⁇ and ⁇ I: inorganic value ⁇ and the hydrophobicity of compounds 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 (pka value) of functional groups, 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 dye ink composition (ink for inkjet) 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 an ionic hydrophilic group (preferably an acidic group, more preferably a sulfo group (-SO 3 M), a carboxy group (-CO 2 M), and a phosphoric acid group (-PO (OM)).
• a hydroxy group an alkylcarbonylamino group, an arylcarbonylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, a quaternary ammonium group and the like.
• a 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 compound represented by the general formula (II) preferably has at least one ionic hydrophilic group.
• M represents a hydrogen atom or a counter cation.
• the counter cation is not particularly limited, and examples thereof include alkali metal ion, ammonium ion, and organic cation (tetramethylammonium, guanidinium, pyridinium, etc.).
• M is preferably a hydrogen atom, an ammonium ion or an alkali metal 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.
• the counter cation may be a single salt or a mixed salt.
• 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.
• R 21 to R 28 independently represent a hydrogen atom or a substituent, and examples of the substituent include a substituent selected from the above-mentioned Substituent Group A.
• Substituents include alkyl groups, aryl groups, aralkyl groups, heterocyclic groups, alkoxy groups, aryloxy groups, hydroxy groups, amino groups (including anilino groups and heterocyclic amino groups), acyl groups, acylamino groups and ureido groups.
• 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 examples of the substituent include a substituent selected from the above-mentioned Substituent Group A.
• Substituents include alkyl groups, aryl groups, aralkyl groups, heterocyclic groups, alkoxy groups, aryloxy groups, hydroxy groups, amino groups (including anilino groups and heterocyclic amino groups), acyl groups, acylamino groups and ureido groups. , Halogen atom, sulfamoyl group, carbamoyl group, sulfonamide group, sulfonyl group, sulfenyl group, sulfinyl group, hydrophilic group and the like, and these may further have a substituent.
• 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).
• 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 content of the compound represented by the general formula (II) in the dye ink composition of the present invention is 0.1 based on the total mass of the dye ink composition. It is preferably ⁇ 10.0% by mass, more preferably 0.3 to 5.0% by mass, further preferably 0.5 to 4.0% by mass, and 0.5 to 3. It is particularly preferably 5% by mass, and most preferably 0.5 to 2.0% by mass. Further, it may be 1.0 to 3.5% by mass depending on the combination of the dye represented by the following general formula (I) and the dye represented by any of (Cy-1) to (Cy-6). It is preferably 1.5 to 2.0% by mass.
• the partial azaphthalocyanine dye represented by the general formula (I) and the compound represented by the general formula (II) coexist in the dye ink composition after the printed matter is formed while ensuring the ejection reliability of the dye ink composition.
• 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 dye ink composition of the present invention may contain a chelating agent.
• a chelating agent (also referred to as a "chelating agent”) is a compound that binds to an inorganic or metal cation (particularly preferably a polyvalent cation) to produce a chelating compound.
• the chelating agent has a function of preventing the formation and growth of insoluble precipitated foreign substances in an aqueous ink composition derived from an inorganic or metal cation (particularly a polyvalent cation) (that is, functions as a solubilizer).
• the dye ink composition (water-based ink composition) of the present invention can suppress the generation of precipitated foreign substances even during long-term storage of the water-based ink composition, and the water-based ink composition after long-term storage.
• a chelating agent that can be used in the present invention is not particularly limited, and various chelating agents can be used.
• inkjet recording inks are undergoing a transition from cartridge inks to large-capacity ink tank models, and have further performance in terms of storage stability during long-term storage, as well as printing quality and ejection stability of ink after long-term storage. Improvement is required, and the dye ink composition of the present invention contains a chelating agent, so that the ink composition is excellent in storage stability during long-term storage, and ink printing quality and ejection stability after long-term storage. Can be used as ink.
• a chelating agent it is possible to form a complex with a cation existing in a dye ink composition (water-based ink composition) by a chelating action, and to suppress the generation and growth of precipitated foreign substances in the water-based ink composition.
• solubilizers can be used alone or in combination of two or more, but a water-soluble compound is preferable.
• chelating agent examples include ethylenediaminetetraacetic acid (EDTA) or a salt thereof (for example, EDTA-4 sodium (4 sodium salt), EDTA-4 lithium (4 lithium salt), etc.), picolinic acid or a salt thereof (for example, picolin).
• EDTA ethylenediaminetetraacetic acid
• a salt thereof for example, EDTA-4 sodium (4 sodium salt), EDTA-4 lithium (4 lithium salt), etc.
• picolinic acid or a salt thereof for example, picolin.
• quinophosphate or a salt thereof eg, sodium quinophosphate
• 1,10-phenanthroline, 8-hydroxyquinoline 3-hydroxy-2,2'-iminodicohactate tetrasodium, methylglycine diacetic acid (MGDA) or Its salt
• L-glutamic acid diacetic acid (GLDA) or its salt L-aspartic acid diacetic acid (ASDA) or its salt
• HIDA hydroxyethyliminodiacetic acid
• HIDS acid
• CMGA dicarboxymethyl glutamic acid
• EDDS -ethylenediaminediaminediaminedic acid
• salts for example, in addition to monovalent metal salts such as sodium, potassium and lithium, salts such as ammonium and amine are preferable.
• these have even smaller attenuation of the chelating action with respect to the pH change of the dye ink composition. Therefore, the chelating action is exhibited in a wider range of pH, and it is possible to further improve the responsiveness of the dye ink composition to pH changes such as changes over time.
• the content of the chelating agent is preferably 0.001% by mass or more and 1.1% by mass or less based on the total mass of the dye ink composition. More preferably, it is 0.001% by mass or more and 0.5% by mass or less, further preferably 0.001% by mass or more and 0.3% by mass or less, and particularly preferably 0.001% by mass or more and 0. It is 1% by mass or less. If it is 0.001% by mass or more, the chelating action can be effectively exhibited, and if it is 1.1% by mass or less, the viscosity of the dye ink composition is excessively increased by the addition of the chelating agent. Or, it is possible to suppress an excessive increase in pH.
• the ratio of the chelating agent to the dye (mass-based content of the chelating agent: mass-based content of the dye) in the dye ink composition is in the range of 0.0001: 1 to 0.15: 1. It is preferably present (the chelating agent / dye is preferably 0.0001 to 0.15). It is more preferably in the range of 0.0001: 1 to 0.01: 1, and even more preferably in the range of 0.0002: 1 to 0.005: 1.
• Metal salts can be formed by metals that can be mixed in during the dye manufacturing process or contained in the ink container of the dye ink composition and eluted into the dye ink composition. With the above ratio, it is possible to effectively suppress the generation of foreign matter that causes clogging of the inkjet head. In addition, the chelating action can be effectively expressed, and it is possible to suppress an excessive increase in the viscosity of the dye ink composition and an excessive increase in pH.
• inventions include an image recording material for forming an image, and specifically, a heat-sensitive recording material and a pressure-sensitive recording material, including an inkjet recording material described in detail below.
• image recording material for forming an image
• a heat-sensitive recording material and a pressure-sensitive recording material including an inkjet recording material described in detail below.
• recording materials using an electrophotographic method transfer type silver halide photosensitive materials, printing inks, recording pens, etc.
• inkjet recording materials thermal recording materials, recording materials using an electrophotographic method, and more preferably.
• the dye ink composition of the present invention records and reproduces a color image used in a solid-state image sensor such as a CCD (Charge-Coupled Device) or a display such as an LCD (Liquid Crystal Display) or a PDP (Plasma Display Panel). It can also be applied to a color filter for dyeing and a dyeing liquid for dyeing various fibers.
• a solid-state image sensor such as a CCD (Charge-Coupled Device) or a display such as an LCD (Liquid Crystal Display) or a PDP (Plasma Display Panel). It can also be applied to a color filter for dyeing and a dyeing liquid for dyeing various fibers.
• the dye ink composition of the present invention can be used by adjusting physical properties such as solubility, dispersibility, and heat transfer suitable for the intended use with a substituent. Further, the dye used in the present invention can be used in a dissolved state, an emulsified dispersed state, or even a solid dispersed state depending on the system used.
• the dye ink composition of the present invention is particularly suitable as a dye ink for inkjet recording.
• the dye ink composition of the present invention uses water as a medium, and if necessary, further uses a lipophilic medium or an aqueous medium to dissolve and / or add a colorant, a toning agent, and an additive in them. It can be produced by dispersing.
• water include pure water such as deionized water, ion-exchanged water, ultrafiltered water, reverse osmosis water, distilled water, and ultrapure water.
• the dye ink composition of the present invention may contain other solvents in addition to water.
• a water-miscible organic solvent is preferable.
• water-miscible organic solvents include alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol), polyhydric alcohols.
• Classes 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 glycol Diacetate, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol monophenyl ether), amines (eg ethanol
• the water content is preferably 40 to 80% by mass, more preferably 45 to 70% by mass, and 50 to 50 to 70% by mass, based on the total mass of the ink composition. It is more preferably 60% by mass from the viewpoint of ink ejection stability and storage stability.
• the content of the water-miscible organic solvent is preferably 10 to 55% by mass based on the total mass of the ink composition. It is more preferably 20 to 50% by mass, and even more preferably 30 to 45% by mass.
• the dye ink of the present invention may contain other additives as necessary within a range that does not impair the effects of the present invention.
• 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.
• wetting agents wetting agents
• anti-fading agents emulsion stabilizers
• penetration promoters emulsion stabilizers
• UV absorbers preservatives
• fungicides fungicides
• pH regulators e.g., pH regulators, surface tension regulators, defoamers.
• foaming agents e.g., foaming agents, viscosity regulators, dispersants, dispersion stabilizers, rust preventives, and betaines (described in JP-A-2003-306623) can be mentioned.
• Examples of the surface tension adjusting agent include nonionic, cationic or anionic surfactants.
• surfactants include fatty acid salts, alkyl sulfates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphates, naphthalene sulfonic acid formalin 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 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.
• the preservative refers to an agent having a function of preventing the growth and growth of microorganisms, particularly bacteria and fungi (molds).
• preservatives include inorganic preservatives containing heavy metal ions and organic preservatives.
• Organic preservatives include quaternary ammonium salts (tetrabutylammonium chloride, cetylpyridinium chloride, benzyltrimethylammonium chloride, etc.), phenols (phenols, cresols, butylphenols, xylenols, bisphenols, etc.), phenoxyether derivatives (phenoxyethanol, etc.).
• heterocyclic compounds (benzotriazole, 1,2-benzoisothiazolin-3-one, sodium dehydroacetate, Proxel® series manufactured by LONZA Co., Ltd., etc.), alkanediols (pentylene glycol (1,) 2-Pentanediol), isopentyldiol (3-methyl-1,3-butanediol), hexanediol (1,2-hexanediol), etc.), caprylyl glycol (1,2-octanediol), etc.), acid Amidos, carbamates, carbamates, amidin / guanidines, pyridines (sodium pyridinethion-1-oxide, etc.), diazines, triazines, pyrrole / imidazoles, oxazole / oxazines, thiazole / thiadiazines, thiourea.
• Various substances such as an ester and a salt thereof (p-hydroxybenzoic acid ethyl ester, etc.) can be used.
• the preservative is preferably at least one selected from the group consisting of heterocyclic compounds, phenols, phenoxy ether derivatives, and alkanediols, and more preferably a heterocyclic compound.
• the antibacterial and antifungal handbook (Gihodo: 1986), the antibacterial and antifungal agent encyclopedia (edited by the Japanese Society of Antibacterial and Antifungal Encyclopedia Editorial Committee) and the like can be used.
• Various compounds such as those having an oil-soluble structure and those having a water-soluble structure can be used as these compounds, but a water-soluble compound is preferable. It may contain two or more preservatives.
• the heterocyclic compound is preferably a thiazole-based compound or a benzotriazole-based compound.
• the thiazole-based compound functions as a fungicide.
• thiazole compounds include benzisothiazolin, isothiazolinone, 1,2-benzisothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 2- (thiocyanomethylthio) benzthiazole, 2- Examples thereof include mercaptobenzthiazole and 3-allyloxy-1,2-benzisothiazolin-1,1-oxide.
• Proxel registered trademark
• LONZA Co., Ltd. can also be used as a thiazole-based fungicide.
• the benzotriazole-based compound functions as a rust preventive, and for example, the metal material (particularly 42 alloy (nickel-iron alloy containing 42% nickel)) constituting the inkjet head is used as an ink. It is possible to prevent the occurrence of rust caused by the contact of the metal.
• the benzotriazole-based compound include 1H-benzotriazole, 4-methyl-1H-benzotriazole, 5-methyl-1H-benzotriazole, and sodium salts or potassium salts thereof.
• the content of the preservative in the dye ink composition of the present invention is not particularly limited and can be used in a wide range, but is preferably 0.001 to 10% by mass, more preferably 0.001 to 10% by mass, based on the total amount of the dye ink composition. It is 0.005 to 2.0% by mass, more preferably 0.01 to 0.5% by mass, and particularly preferably 0.01 to 0.1% by mass. By setting the content to 0.001 to 10% by mass, the effect of the preservative can be obtained more efficiently, and the generation of precipitates can be suppressed.
• the inkjet recording method of the present invention supplies energy to the dye ink for inkjet recording of the present invention to provide a known image receiving material, that is, plain paper or resin-coated paper, for example, JP-A-8-169172, No. 8-27693.
• a known image receiving material that is, plain paper or resin-coated paper, for example, JP-A-8-169172, No. 8-27693.
• Japanese Patent Application Laid-Open No. 2-276670, 7-276789, 9-323475 Japanese Patent Application Laid-Open No. 62-238783, Japanese Patent Application Laid-Open No. 10-153989, Japanese Patent Application Laid-Open No. 10-217473, 10- Images are printed on inkjet paper, film, electrophotographic paper, cloth, glass, metal, ceramics, etc. described in 235995, 10-33747, 10-217597, 10-33747, etc. Form.
• a polymer latex compound When forming an image, a polymer latex compound may be used in combination for the purpose of imparting glossiness and water resistance and improving weather resistance.
• the recording method of the inkjet recording method of the present invention there is no limitation on the recording method of the inkjet recording method of the present invention, and there is no limitation on the recording method, for example, a charge control method for ejecting ink by using electrostatic attraction, and a drop-on-demand method (pressure) using the vibration pressure of the piezo element.
• a charge control method for ejecting ink by using electrostatic attraction and a drop-on-demand method (pressure) using the vibration pressure of the piezo element.
• Pulse method an acoustic inkjet method that converts an electric signal into an acoustic beam and irradiates the ink to eject the ink using the radiation pressure
• a thermal inkjet method that heats the ink to form bubbles and uses the generated pressure. It is used for methods and the like.
• a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving image quality by using a plurality of inks having substantially the same hue but different densities, and a colorless and transparent ink are used. The method is included.
• the surface tension of the dye ink composition of the present invention at 25 ° C. is preferably 10 mN / m or more and 60 mN / m or less, more preferably 20 mN / m or more and 60 mN / m or less, and 30 mN / m or more and 40 mN / m or less. It is more preferably m or less.
• the surface tension of the ink can be adjusted by appropriately determining the content of the surfactant or the like in the dye ink composition. Further, the dye ink composition of the present invention is preferably adjusted to a desired pH so that good ejection characteristics can be obtained when applied to an inkjet recording device.
• the viscosity of the dye ink composition of the present invention at 25 ° C. is preferably 1.0 mPa ⁇ s or more and 5.0 mPa ⁇ s or less.
• the dye ink composition of the present invention is preferable because it can be stored in an ink cartridge and used, and it is convenient to handle.
• Ink cartridges are known in the art and can be made into ink cartridges by appropriately using known methods. Further, the ink cartridge can be used for an inkjet printer.
• the ink cartridge can be used for general writing instruments, recorders, pen plotters, etc., but it is particularly preferable to use it for an inkjet recording method.
• the inkjet recording method of the present invention includes an image recording step of ejecting a dye ink for inkjet recording containing the dye ink composition of the present invention described above by an inkjet recording head and recording an image on a recording medium. Then, in the image recording step, in addition to the dye ink composition of the present invention (preferably cyan dye ink composition) described above, a magenta dye ink composition, a yellow dye ink composition, and a black dye ink composition are inked. It can be used as a set. Further, the inkjet recording apparatus of the present invention is an apparatus including an ink accommodating portion for accommodating dye ink and a recording head for ejecting ink.
• the dye ink contained in the ink container is the cyan dye ink composition of the present invention, the magenta ink composition, the yellow ink composition, and the black ink composition described above.
• the steps and configurations of the inkjet recording method and the recording device may be known.
• any one that can be used for general inkjet can be used.
• Examples of such a recording medium include a recording medium for an inkjet having a porous layer on a support such as glossy paper, coated paper, and glossy film, and so-called copy paper in which fibers are exposed on at least a part of the surface. Plain paper can be mentioned.
• Example 1 (Preparation of Cyan Dye Ink Composition 1) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 1 (100 g).
• Cyan dye (P-5) 1.69g Cyan dye (mixture of P-32-1 to P-32-4) 0.85 g Cyan dye (mixture of P-45-1 to P-45-4) 0.19 g Cyan dye (C-1) 1.27g Additive (A-4) 0.50 g
• Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• the preservative is Proxel® XL2 (s) manufactured by LONZA Co., Ltd. The same applies to the preservatives used in the following examples and comparative examples.
• the above-mentioned surfactant is Surfinol (registered trademark) 465 manufactured by Nissin Chemical Industry Co., Ltd. The same applies to the surfactants used in the following examples and comparative examples.
• Example 2 (Preparation of Cyan Dye Ink Composition 2) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 2 (100 g).
• Cyan dye (P-11) 1.69g Cyan dye (mixture of P-36-1 to P-36-4) 0.85 g Cyan dye (mixture of P-46-1 to P-46-4) 0.19 g Cyan dye (C-12) 1.27 g Additive (A-3) 0.50 g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 3 (Preparation of Cyan Dye Ink Composition 3) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 3 (100 g).
• Cyan dye (P-6) 1.69g Cyan dye (mixture of P-33-1 to P-33-4) 0.85 g Cyan dye (mixture of P-47-1 to P-47-4) 0.19 g Cyan dye (C-1) 1.27g Additive (A-4) 0.50 g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 4 (Preparation of Cyan Dye Ink Composition 4)
• Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 4 (100 g).
• Cyan dye (P-12) 1.69g Cyan dye (mixture of P-38-1 to P-38-4) 0.85 g Cyan dye (mixture of P-48-1 to P-48-4) 0.19 g Cyan dye (C-12) 1.27 g Additive (A-3) 0.50 g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 5 (Preparation of Cyan Dye Ink Composition 5) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 5 (100 g).
• Cyan dye (P-7) 1.69g Cyan dye (mixture of P-34-1 to P-34-2) 0.85 g Cyan dye (P-59) 0.19g Cyan dye (C-1) 1.27g Additive (A-4) 0.50 g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 6 (Preparation of Cyan Dye Ink Composition 6)
• Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 6 (100 g).
• Cyan dye (P-5) 1.69g Cyan dye (mixture of P-32-1 to P-32-4) 0.85 g Cyan dye (mixture of P-45-1 to P-45-4) 0.19 g Cyan dye (C-1) 1.27g Additive (A-4) 1.00 g
• Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 7 (Preparation of Cyan Dye Ink Composition 7)
• Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 7 (100 g).
• Cyan dye (P-11) 1.69g Cyan dye (mixture of P-36-1 to P-36-4) 0.85 g Cyan dye (mixture of P-46-1 to P-46-4) 0.19 g Cyan dye (C-12) 1.27 g Additive (A-3) 1.00 g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 8 (Preparation of Cyan Dye Ink Composition 8) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 8 (100 g).
• Cyan dye (P-6) 1.69g Cyan dye (mixture of P-33-1 to P-33-4) 0.85 g Cyan dye (mixture of P-47-1 to P-47-4) 0.19 g Cyan dye (C-1) 1.27g Additive (A-4) 1.00 g
• Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 9 (Preparation of Cyan Dye Ink Composition 9) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 9 (100 g).
• Cyan dye (P-12) 1.69g Cyan dye (mixture of P-38-1 to P-38-4) 0.85 g Cyan dye (mixture of P-48-1 to P-48-4) 0.19 g Cyan dye (C-12) 1.27 g Additive (A-3) 1.00 g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 10 (Preparation of Cyan Dye Ink Composition 10) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 10 (100 g).
• Cyan dye (P-7) 1.69g Cyan dye (mixture of P-34-1 to P-34-2) 0.85 g Cyan dye (P-59) 0.19g Cyan dye (C-1) 1.27g Additive (A-4) 1.00 g
• Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 11 (Preparation of Cyan Dye Ink Composition 11) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 11 (100 g).
• Cyan dye (P-5) 1.69g Cyan dye (mixture of P-32-1 to P-32-4) 0.85 g Cyan dye (mixture of P-45-1 to P-45-4) 0.19 g Cyan dye (C-1) 1.27g Additive (A-4) 1.50 g
• Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 12 (Preparation of Cyan Dye Ink Composition 12) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 12 (100 g).
• Cyan dye (P-11) 1.69g Cyan dye (mixture of P-36-1 to P-36-4) 0.85 g Cyan dye (mixture of P-46-1 to P-46-4) 0.19 g Cyan dye (C-12) 1.27 g Additive (A-3) 1.50 g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 13 (Preparation of Cyan Dye Ink Composition 13) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 13 (100 g).
• Cyan dye (P-6) 1.69g Cyan dye (mixture of P-33-1 to P-33-4) 0.85 g Cyan dye (mixture of P-47-1 to P-47-4) 0.19 g Cyan dye (C-1) 1.27g Additive (A-4) 1.50 g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 14 (Preparation of Cyan Dye Ink Composition 14) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 14 (100 g).
• Cyan dye (P-12) 1.69g Cyan dye (mixture of P-38-1 to P-38-4) 0.85 g Cyan dye (mixture of P-48-1 to P-48-4) 0.19 g Cyan dye (C-12) 1.27 g Additive (A-3) 1.50 g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 15 (Preparation of Cyan Dye Ink Composition 15) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 15 (100 g).
• Cyan dye (P-7) 1.69g Cyan dye (mixture of P-34-1 to P-34-2) 0.85 g Cyan dye (P-59) 0.19g Cyan dye (C-1) 1.27g Additive (A-4) 1.50 g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 16 (Preparation of Cyan Dye Ink Composition 16) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 16 (100 g).
• Cyan dye (P-5) 1.69g Cyan dye (mixture of P-32-1 to P-32-4) 0.85 g Cyan dye (mixture of P-45-1 to P-45-4) 0.19 g Cyan dye (C-1) 1.27g Additive (A-4) 2.00 g
• Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 17 (Preparation of Cyan Dye Ink Composition 17) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 17 (100 g).
• Cyan dye (P-11) 1.69g Cyan dye (mixture of P-36-1 to P-36-4) 0.85 g Cyan dye (mixture of P-46-1 to P-46-4) 0.19 g Cyan dye (C-12) 1.27 g Additive (A-3) 2.00 g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 18 (Preparation of Cyan Dye Ink Composition 18) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 18 (100 g).
• Cyan dye (P-6) 1.69g Cyan dye (mixture of P-33-1 to P-33-4) 0.85 g Cyan dye (mixture of P-47-1 to P-47-4) 0.19 g Cyan dye (C-1) 1.27g Additive (A-4) 2.00 g
• Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 19 (Preparation of Cyan Dye Ink Composition 19) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 19 (100 g).
• Cyan dye (P-12) 1.69g Cyan dye (mixture of P-38-1 to P-38-4) 0.85 g Cyan dye (mixture of P-48-1 to P-48-4) 0.19 g Cyan dye (C-12) 1.27 g Additive (A-3) 2.00 g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 20 (Preparation of Cyan Dye Ink Composition 20) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 20 (100 g).
• Cyan dye (P-7) 1.69g Cyan dye (mixture of P-34-1 to P-34-2) 0.85 g Cyan dye (P-59) 0.19g Cyan dye (C-1) 1.27g Additive (A-4) 2.00 g
• Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 21 (Preparation of Cyan Dye Ink Composition 21) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 21 (100 g).
• Cyan dye (P-18) 1.69g Cyan dye (mixture of P-41-1 to P-41-1) 0.85 g Cyan dye (mixture of P-53-1 to P-53-4) 0.19 g Cyan dye (C-10) 1.27g Additive (A-4) 1.00 g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 22 (Preparation of Cyan Dye Ink Composition 22) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 22 (100 g).
• Cyan dye (P-19) 1.69g Cyan dye (mixture of P-42-1 to P-42-4) 0.85 g Cyan dye (mixture of P-55-1 to P-55-4) 0.19 g Cyan dye (C-10) 1.27g Additive (A-4) 1.00 g
• Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 23 (Preparation of Cyan Dye Ink Composition 23) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 23 (100 g).
• Cyan dye (P-20) 1.69g Cyan dye (mixture of P-43-1 to P-43-4) 0.85 g Cyan dye (mixture of P-57-1 to P-57-4) 0.19 g Cyan dye (C-11) 1.27 g Additive (A-4) 1.00 g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 24 (Preparation of Cyan Dye Ink Composition 24) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 24 (100 g).
• Cyan dye (P-22) 1.69g Cyan dye (mixture of P-39-1 to P-39-4) 0.85 g Cyan dye (mixture of P-49-1 to P-49-4) 0.19 g Cyan dye (C-16) 1.27g Additive (A-4) 1.00 g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 25 (Preparation of Cyan Dye Ink Composition 25) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 25 (100 g).
• Example 26 (Preparation of Cyan Dye Ink Composition 26) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 26 (100 g).
• Cyan dye (P-5) 1.07g Cyan dye (mixture of P-32-1 to P-32-4) 1.60 g Cyan dye (mixture of P-45-1 to P-45-4) 1.07 g Cyan dye (C-1) 0.26g Additive (A-4) 1.50 g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 27 (Preparation of Cyan Dye Ink Composition 27) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 27 (100 g).
• Cyan dye (P-11) 1.07g Cyan dye (mixture of P-36-1 to P-36-4) 1.60 g Cyan dye (mixture of P-46-1 to P-46-4) 1.07 g Cyan dye (C-12) 0.26g
• Additive (A-3) 1.50 g
• Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g
• Example 28 (Preparation of Cyan Dye Ink Composition 28) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 28 (100 g).
• Cyan dye (P-6) 1.07g Cyan dye (mixture of P-33-1 to P-33-4) 1.60 g Cyan dye (mixture of P-47-1 to P-47-4) 1.07 g Cyan dye (C-1) 0.26g Additive (A-4) 1.50 g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 29 (Preparation of Cyan Dye Ink Composition 29) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 29 (100 g).
• Cyan dye (P-12) 1.07g Cyan dye (mixture of P-38-1 to P-38-4) 1.60 g Cyan dye (mixture of P-48-1 to P-48-4) 1.07 g Cyan dye (C-12) 0.26g Additive (A-3) 1.50 g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 30 (Preparation of Cyan Dye Ink Composition 30) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 30 (100 g).
• Cyan dye (P-7) 1.07g Cyan dye (mixture of P-34-1 to P-34-2) 1.60 g Cyan dye (P-59) 1.07 g Cyan dye (C-1) 0.26g Additive (A-4) 1.50 g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 31 (Preparation of Cyan Dye Ink Composition 31) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 31 (100 g).
• Cyan dye (P-5) 2.11g Cyan dye (mixture of P-32-1 to P-32-4) 1.06 g Cyan dye (mixture of P-45-1 to P-45-4) 0.24 g Cyan dye (C-1) 1.59g Additive (A-4) 1.50 g
• Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 32 (Preparation of Cyan Dye Ink Composition 32) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 32 (100 g).
• Cyan dye (P-11) 2.11g Cyan dye (mixture of P-36-1 to P-36-4) 1.06 g Cyan dye (mixture of P-46-1 to P-46-4) 0.24 g Cyan dye (C-12) 1.59g Additive (A-3) 1.50 g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 33 (Preparation of Cyan Dye Ink Composition 33) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 33 (100 g).
• Cyan dye (P-6) 2.11g Cyan dye (mixture of P-33-1 to P-33-4) 1.06 g Cyan dye (mixture of P-47-1 to P-47-4) 0.24 g Cyan dye (C-1) 1.59g Additive (A-4) 1.50 g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 34 (Preparation of Cyan Dye Ink Composition 34) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 34 (100 g).
• Cyan dye (P-12) 2.11g Cyan dye (mixture of P-38-1 to P-38-4) 1.06 g Cyan dye (mixture of P-48-1 to P-48-4) 0.24 g Cyan dye (C-12) 1.59g Additive (A-3) 1.50 g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 35 (Preparation of Cyan Dye Ink Composition 35) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 35 (100 g).
• Cyan dye (P-7) 2.11g Cyan dye (mixture of P-34-1 to P-34-2) 1.06 g Cyan dye (P-59) 0.24g Cyan dye (C-1) 1.59g Additive (A-4) 1.50 g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 36 (Preparation of Cyan Dye Ink Composition 36) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 36 (100 g).
• Cyan dye (P-18) 2.11g Cyan dye (mixture of P-41-1 to P-41-1) 1.06 g Cyan dye (mixture of P-53-1 to P-53-4) 0.24 g Cyan dye (C-10) 1.59g Additive (A-4) 1.50 g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 37 (Preparation of Cyan Dye Ink Composition 37) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 37 (100 g).
• Cyan dye (P-19) 2.11g Cyan dye (mixture of P-42-1 to P-42-4) 1.06 g Cyan dye (mixture of P-55-1 to P-55-4) 0.24 g Cyan dye (C-10) 1.59g Additive (A-4) 1.50 g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 38 (Preparation of Cyan Dye Ink Composition 38) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 38 (100 g).
• Cyan dye (P-20) 2.11g Cyan dye (mixture of P-43-1 to P-43-4) 1.06 g Cyan dye (mixture of P-57-1 to P-57-4) 0.24 g Cyan dye (C-11) 1.59g
• Additive (A-4) 1.50 g
• Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g
• Example 39 (Preparation of Cyan Dye Ink Composition 39) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 39 (100 g).
• Cyan dye (P-22) 2.11g Cyan dye (mixture of P-39-1 to P-39-4) 1.06 g Cyan dye (mixture of P-49-1 to P-49-4) 0.24 g Cyan dye (C-16) 1.59g Additive (A-4) 1.50 g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 40 (Preparation of Cyan Dye Ink Composition 40) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 40 (100 g).
• Cyan dye (P-23) 2.11g Cyan dye (mixture of P-40-1 to P-40-4) 1.06 g Cyan dye (mixture of P-51-1 to P-51-4) 0.24 g Cyan dye (C-16) 1.59g Additive (A-4) 1.50 g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 41 (Preparation of Cyan Dye Ink Composition 41) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 41 (100 g).
• Cyan dye (P-5) 1.27g Cyan dye (mixture of P-32-1 to P-32-4) 0.64 g Cyan dye (mixture of P-45-1 to P-45-4) 0.13 g Cyan dye (C-1) 0.96 g Additive (A-4) 1.00 g
• Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 42 (Preparation of Cyan Dye Ink Composition 42) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 42 (100 g).
• Cyan dye (P-11) 1.27g Cyan dye (mixture of P-36-1 to P-36-4) 0.64 g Cyan dye (mixture of P-46-1 to P-46-4) 0.13 g Cyan dye (C-12) 0.96g
• Additive (A-3) 1.00 g
• Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 43 (Preparation of Cyan Dye Ink Composition 43) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 43 (100 g).
• Cyan dye (P-6) 1.27g Cyan dye (mixture of P-33-1 to P-33-4) 0.64 g Cyan dye (mixture of P-47-1 to P-47-4) 0.13 g Cyan dye (C-1) 0.96 g Additive (A-4) 1.00 g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 44 (Preparation of Cyan Dye Ink Composition 44) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 44 (100 g).
• Cyan dye (P-12) 1.27g Cyan dye (mixture of P-38-1 to P-38-4) 0.64 g Cyan dye (mixture of P-48-1 to P-48-4) 0.13 g Cyan dye (C-12) 0.96g Additive (A-3) 1.00 g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 45 (Preparation of Cyan Dye Ink Composition 45) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 45 (100 g).
• Cyan dye (P-7) 1.27g Cyan dye (mixture of P-34-1 to P-34-2) 0.64 g Cyan dye (P-59) 0.13g Cyan dye (C-1) 0.96 g Additive (A-4) 1.00 g
• Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 46 (Preparation of Cyan Dye Ink Composition 46) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 46 (100 g).
• Cyan dye (P-18) 1.27g Cyan dye (mixture of P-41-1 to P-41-1) 0.64 g Cyan dye (mixture of P-53-1 to P-53-4) 0.13 g Cyan dye (C-10) 0.96g Additive (A-4) 1.00 g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 47 (Preparation of Cyan Dye Ink Composition 47) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 47 (100 g).
• Cyan dye (P-19) 1.27g Cyan dye (mixture of P-42-1 to P-42-4) 0.64 g Cyan dye (mixture of P-55-1 to P-55-4) 0.13 g Cyan dye (C-10) 0.96g Additive (A-4) 1.00 g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 48 (Preparation of Cyan Dye Ink Composition 48) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 48 (100 g).
• Cyan dye (P-20) 1.27g Cyan dye (mixture of P-43-1 to P-43-4) 0.64 g Cyan dye (mixture of P-57-1 to P-57-4) 0.13 g Cyan dye (C-11) 0.96g
• Additive (A-4) 1.00 g
• Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 49 (Preparation of Cyan Dye Ink Composition 49) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 49 (100 g).
• Cyan dye (P-22) 1.27g Cyan dye (mixture of P-39-1 to P-39-4) 0.64 g Cyan dye (mixture of P-49-1 to P-49-4) 0.13 g Cyan dye (C-16) 0.96g Additive (A-4) 1.00 g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 50 (Preparation of Cyan Dye Ink Composition 50) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 50 (100 g).
• Cyan dye (P-23) 1.27g Cyan dye (mixture of P-40-1 to P-40-4) 0.64 g Cyan dye (mixture of P-51-1 to P-51-4) 0.13 g Cyan dye (C-16) 0.96g
• Additive (A-4) 1.00 g
• Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 51 (Preparation of Cyan Dye Ink Composition 51) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 51 (100 g).
• Cyan dye (P-5) 1.52g Cyan dye (mixture of P-32-1 to P-32-4) 0.77 g Cyan dye (mixture of P-45-1 to P-45-4) 0.17 g Cyan dye (C-1) 1.14g Cyan dye (C-41) 0.40 g Additive (A-4) 1.00 g
• Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 52 (Preparation of Cyan Dye Ink Composition 52) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 52 (100 g).
• Example 53 (Preparation of Cyan Dye Ink Composition 53) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 53 (100 g).
• Cyan dye (P-6) 1.52g Cyan dye (mixture of P-33-1 to P-33-4) 0.77 g Cyan dye (mixture of P-47-1 to P-47-4) 0.17 g Cyan dye (C-1) 1.14g Cyan dye (C-41) 0.40 g Additive (A-4) 1.00 g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 54 (Preparation of Cyan Dye Ink Composition 54) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 54 (100 g).
• Example 55 (Preparation of Cyan Dye Ink Composition 55) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 55 (100 g).
• Cyan dye (P-7) 1.52g Cyan dye (mixture of P-34-1 to P-34-2) 0.77 g Cyan dye (P-59) 0.17g Cyan dye (C-1) 1.14g Cyan dye (C-41) 0.40 g Additive (A-4) 1.00 g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 56 (Preparation of Cyan Dye Ink Composition 56) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 56 (100 g).
• Cyan dye (P-5) 1.52g Cyan dye (mixture of P-32-1 to P-32-4) 0.77 g Cyan dye (mixture of P-45-1 to P-45-4) 0.17 g Cyan dye (C-1) 1.14g Cyan dye (C-41) 0.20 g C. I.
• Example 57 (Preparation of Cyan Dye Ink Composition 57) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 57 (100 g).
• Cyan dye (P-6) 1.52g Cyan dye (mixture of P-33-1 to P-33-4) 0.77 g Cyan dye (mixture of P-47-1 to P-47-4) 0.17 g Cyan dye (C-1) 1.14g Cyan dye (C-41) 0.20 g C. I.
• Example 58 (Preparation of Cyan Dye Ink Composition 58) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 58 (100 g).
• Cyan dye (P-7) 1.52g Cyan dye (mixture of P-34-1 to P-34-2) 0.77 g Cyan dye (P-59) 0.17g Cyan dye (C-1) 1.14g Cyan dye (C-41) 0.20 g C. I.
• Example 59 (Preparation of Cyan Dye Ink Composition 59) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 59 (100 g).
• Cyan dye (P-5) 1.52g Cyan dye (mixture of P-32-1 to P-32-4) 0.77 g Cyan dye (mixture of P-45-1 to P-45-4) 0.17 g Cyan dye (C-1) 1.14g Cyan dye (C-41) 0.20 g C. I.
• Example 60 (Preparation of Cyan Dye Ink Composition 60) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 60 (100 g).
• Cyan dye (P-6) 1.52g Cyan dye (mixture of P-33-1 to P-33-4) 0.77 g Cyan dye (mixture of P-47-1 to P-47-4) 0.17 g Cyan dye (C-1) 1.14g Cyan dye (C-41) 0.20 g C. I.
• Example 61 (Preparation of Cyan Dye Ink Composition 61) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 61 (100 g).
• Cyan dye (P-5) 1.52g Cyan dye (mixture of P-32-1 to P-32-4) 0.77 g Cyan dye (mixture of P-45-1 to P-45-4) 0.17 g Cyan dye (C-1) 1.14g C. I.
• Example 62 (Preparation of Cyan Dye Ink Composition 62) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 62 (100 g).
• Example 63 (Preparation of Cyan Dye Ink Composition 63) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 63 (100 g).
• Cyan dye (P-6) 1.52g Cyan dye (mixture of P-33-1 to P-33-4) 0.77 g Cyan dye (mixture of P-47-1 to P-47-4) 0.17 g Cyan dye (C-1) 1.14g C. I.
• Example 64 (Preparation of Cyan Dye Ink Composition 64) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 64 (100 g).
• Example 65 (Preparation of Cyan Dye Ink Composition 65) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 65 (100 g).
• Example 66 (Preparation of Cyan Dye Ink Composition 66) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 66 (100 g).
• Cyan dye (P-5) 1.52g Cyan dye (mixture of P-32-1 to P-32-4) 0.77 g Cyan dye (mixture of P-45-1 to P-45-4) 0.17 g Cyan dye (C-1) 1.14g C. I.
• Example 67 (Preparation of Cyan Dye Ink Composition 67) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 67 (100 g).
• Example 68 (Preparation of Cyan Dye Ink Composition 68) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 68 (100 g).
• Cyan dye (P-6) 1.52g Cyan dye (mixture of P-33-1 to P-33-4) 0.77 g Cyan dye (mixture of P-47-1 to P-47-4) 0.17 g Cyan dye (C-1) 1.14g C. I.
• Example 69 (Preparation of Cyan Dye Ink Composition 69) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 69 (100 g).
• Example 70 (Preparation of Cyan Dye Ink Composition 70) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 70 (100 g).
• Example 71 (Preparation of Cyan Dye Ink Composition 71) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 71 (100 g).
• Cyan dye (P-5) 1.69g Cyan dye (mixture of P-32-1 to P-32-4) 0.85 g Cyan dye (mixture of P-45-1 to P-45-4) 0.19 g Cyan dye (C-1) 1.27g Additive (A-4) 0.50 g Preservative 0.11g Glycerin 7.00g Ethylene urea 7.00g 1,5-pentanediol 7.00g 2-Pyrrolidone 5.00g Surfactant 0.50g
• Example 72 (Preparation of Cyan Dye Ink Composition 72) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 72 (100 g).
• Cyan dye (P-11) 1.69g Cyan dye (mixture of P-36-1 to P-36-4) 0.85 g Cyan dye (mixture of P-46-1 to P-46-4) 0.19 g Cyan dye (C-12) 1.27 g Additive (A-3) 0.50 g Preservative 0.11g Glycerin 7.00g Ethylene urea 7.00g 1,5-pentanediol 7.00g 2-Pyrrolidone 5.00g Surfactant 0.50g
• Example 73 (Preparation of Cyan Dye Ink Composition 73) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 73 (100 g).
• Cyan dye (P-6) 1.69g Cyan dye (mixture of P-33-1 to P-33-4) 0.85 g Cyan dye (mixture of P-47-1 to P-47-4) 0.19 g Cyan dye (C-1) 1.27g Additive (A-4) 0.50 g Preservative 0.11g Glycerin 7.00g Ethylene urea 7.00g 1,5-pentanediol 7.00g 2-Pyrrolidone 5.00g Surfactant 0.50g
• Example 74 (Preparation of Cyan Dye Ink Composition 74) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 74 (100 g).
• Cyan dye (P-12) 1.69g Cyan dye (mixture of P-38-1 to P-38-4) 0.85 g Cyan dye (mixture of P-48-1 to P-48-4) 0.19 g Cyan dye (C-12) 1.27 g Additive (A-3) 0.50 g Preservative 0.11g Glycerin 7.00g Ethylene urea 7.00g 1,5-pentanediol 7.00g 2-Pyrrolidone 5.00g Surfactant 0.50g
• Example 75 (Preparation of Cyan Dye Ink Composition 75) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 75 (100 g).
• Cyan dye (P-7) 1.69g Cyan dye (mixture of P-34-1 to P-34-2) 0.85 g Cyan dye (P-59) 0.19g Cyan dye (C-1) 1.27g Additive (A-4) 0.50 g
• Example 76 (Preparation of Cyan Dye Ink Composition 76) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 76 (100 g).
• Cyan dye (P-5) 1.69g Cyan dye (mixture of P-32-1 to P-32-4) 0.85 g Cyan dye (mixture of P-45-1 to P-45-4) 0.19 g Cyan dye (C-1) 1.27g Additive (A-4) 1.00 g Preservative 0.11g Glycerin 7.00g Ethylene urea 7.00g 1,5-pentanediol 7.00g 2-Pyrrolidone 5.00g Surfactant 0.50g
• Example 77 (Preparation of Cyan Dye Ink Composition 77) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 77 (100 g).
• Cyan dye (P-11) 1.69g Cyan dye (mixture of P-36-1 to P-36-4) 0.85 g Cyan dye (mixture of P-46-1 to P-46-4) 0.19 g Cyan dye (C-12) 1.27 g Additive (A-3) 1.00 g Preservative 0.11g Glycerin 7.00g Ethylene urea 7.00g 1,5-pentanediol 7.00g 2-Pyrrolidone 5.00g Surfactant 0.50g
• Example 78 (Preparation of Cyan Dye Ink Composition 78) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 78 (100 g).
• Cyan dye (P-6) 1.69g Cyan dye (mixture of P-33-1 to P-33-4) 0.85 g Cyan dye (mixture of P-47-1 to P-47-4) 0.19 g Cyan dye (C-1) 1.27g Additive (A-4) 1.00 g Preservative 0.11g Glycerin 7.00g Ethylene urea 7.00g 1,5-pentanediol 7.00g 2-Pyrrolidone 5.00g Surfactant 0.50g
• Example 79 (Preparation of Cyan Dye Ink Composition 79) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 79 (100 g).
• Cyan dye (P-12) 1.69g Cyan dye (mixture of P-38-1 to P-38-4) 0.85 g Cyan dye (mixture of P-48-1 to P-48-4) 0.19 g Cyan dye (C-12) 1.27 g Additive (A-3) 1.00 g Preservative 0.11g Glycerin 7.00g Ethylene urea 7.00g 1,5-pentanediol 7.00g 2-Pyrrolidone 5.00g Surfactant 0.50g
• Example 80 (Preparation of Cyan Dye Ink Composition 80) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 80 (100 g).
• Cyan dye (P-7) 1.69g Cyan dye (mixture of P-34-1 to P-34-2) 0.85 g Cyan dye (P-59) 0.19g Cyan dye (C-1) 1.27g Additive (A-4) 1.00 g Preservative 0.11g Glycerin 7.00g Ethylene urea 7.00g 1,5-pentanediol 7.00g 2-Pyrrolidone 5.00g Surfactant 0.50g
• Example 81 (Preparation of Cyan Dye Ink Composition 81) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 81 (100 g).
• Example 82 (Preparation of Cyan Dye Ink Composition 82) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 82 (100 g).
• Example 83 (Preparation of Cyan Dye Ink Composition 83) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 83 (100 g).
• Example 84 (Preparation of Cyan Dye Ink Composition 84) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 84 (100 g).
• Example 85 (Preparation of Cyan Dye Ink Composition 85) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 85 (100 g).
• Cyan dye (P-7) 1.52g Cyan dye (mixture of P-34-1 to P-34-2) 0.77 g Cyan dye (P-59) 0.17g Cyan dye (C-1) 1.14g Cyan dye (C-41) 0.20 g C.
• Cyan dye (A-4) 1.00 g
• Example 86 (Preparation of Cyan Dye Ink Composition 86) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 86 (100 g).
• Example 87 (Preparation of Cyan Dye Ink Composition 87) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 87 (100 g).
• Example 88 (Preparation of Cyan Dye Ink Composition 88) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 88 (100 g).
• Example 89 (Preparation of Cyan Dye Ink Composition 89) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 89 (100 g).
• Example 90 (Preparation of Cyan Dye Ink Composition 90) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 90 (100 g).
• Example 91 (Preparation of Cyan Dye Ink Composition 91) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 91 (100 g).
• Example 92 (Preparation of Cyan Dye Ink Composition 92) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 92 (100 g).
• Example 93 (Preparation of Cyan Dye Ink Composition 93) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 93 (100 g).
• Example 94 (Preparation of Cyan Dye Ink Composition 94) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 94 (100 g).
• Example 95 (Preparation of Cyan Dye Ink Composition 95) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 95 (100 g).
• Example 96 (Preparation of Cyan Dye Ink Composition 96) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 71 (100 g).
• Cyan dye (P-5) 1.69g Cyan dye (mixture of P-32-1 to P-32-4) 0.85 g Cyan dye (mixture of P-45-1 to P-45-4) 0.19 g Cyan dye (C-1) 1.27g Additive (A-1) 1.00 g Preservative 0.11g Glycerin 7.00g Ethylene urea 7.00g 1,5-pentanediol 7.00g 2-Pyrrolidone 5.00g Surfactant 0.50g
• Example 97 (Preparation of Cyan Dye Ink Composition 97) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 97 (100 g).
• Cyan dye (P-6) 1.69g Cyan dye (mixture of P-33-1 to P-33-4) 0.85 g Cyan dye (mixture of P-47-1 to P-47-4) 0.19 g Cyan dye (C-1) 1.27g Additive (A-1) 1.00 g Preservative 0.11g Glycerin 7.00g Ethylene urea 7.00g 1,5-pentanediol 7.00g 2-Pyrrolidone 5.00g Surfactant 0.50g
• Example 98 (Preparation of Cyan Dye Ink Composition 98) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 98 (100 g).
• Cyan dye (P-7) 1.69g Cyan dye (mixture of P-34-1 to P-34-2) 0.85 g Cyan dye (P-59) 0.19g Cyan dye (C-1) 1.27g Additive (A-1) 1.00 g Preservative 0.11g Glycerin 7.00g Ethylene urea 7.00g 1,5-pentanediol 7.00g 2-Pyrrolidone 5.00g Surfactant 0.50g
• Example 99 (Preparation of Cyan Dye Ink Composition 99) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 99 (100 g).
• Cyan dye (P-5) 1.69g Cyan dye (mixture of P-32-1 to P-32-4) 0.85 g Cyan dye (mixture of P-45-1 to P-45-4) 0.19 g Cyan dye (C-1) 1.27g Additive (A-2) 1.00 g Preservative 0.11g Glycerin 7.00g Ethylene urea 7.00g 1,5-pentanediol 7.00g 2-Pyrrolidone 5.00g Surfactant 0.50g
• Example 100 (Preparation of Cyan Dye Ink Composition 100) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 100 (100 g).
• Cyan dye (P-6) 1.69g Cyan dye (mixture of P-33-1 to P-33-4) 0.85 g Cyan dye (mixture of P-47-1 to P-47-4) 0.19 g Cyan dye (C-1) 1.27g Additive (A-2) 1.00 g Preservative 0.11g Glycerin 7.00g Ethylene urea 7.00g 1,5-pentanediol 7.00g 2-Pyrrolidone 5.00g Surfactant 0.50g
• Example 101 (Preparation of Cyan Dye Ink Composition 101) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 101 (100 g).
• Cyan dye (P-7) 1.69g Cyan dye (mixture of P-34-1 to P-34-2) 0.85 g Cyan dye (P-59) 0.19g Cyan dye (C-1) 1.27g Additive (A-2) 1.00 g Preservative 0.11g Glycerin 7.00g Ethylene urea 7.00g 1,5-pentanediol 7.00g 2-Pyrrolidone 5.00g Surfactant 0.50g
• Example 102 (Preparation of Cyan Dye Ink Composition 102) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 102 (100 g).
• Example 103 (Preparation of Cyan Dye Ink Composition 103) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 103 (100 g).
• Example 104 (Preparation of Cyan Dye Ink Composition 104) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 104 (100 g).
• Example 105 (Preparation of Cyan Dye Ink Composition 105) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 105 (100 g).
• Example 106 (Preparation of Cyan Dye Ink Composition 106) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 106 (100 g).
• Example 107 (Preparation of Cyan Dye Ink Composition 107) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 107 (100 g).
• Cyan dye (P-7) 2.47g Cyan dye (mixture of P-34-1 to P-34-2) 1.24 g Cyan dye (P-59) 0.29g
• Additive (A-4) 1.50 g
• Example 108 (Preparation of Cyan Dye Ink Composition 108) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 108 (100 g).
• Cyan dye (P-1) 1.69g Cyan dye (mixture of P-44-1 to P-44-4) 0.85 g Cyan dye (mixture of P-62-1 to P-62-4) 0.19 g Cyan dye (C-5) 1.27g Additive (A-4) 1.00 g
• Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 109 (Preparation of Cyan Dye Ink Composition 109) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 109 (100 g).
• Cyan dye (P-1) 1.07 g Cyan dye (mixture of P-44-1 to P-44-4) 1.60 g Cyan dye (mixture of P-62-1 to P-62-4) 1.07 g Cyan dye (C-5) 0.26g Additive (A-4) 1.50 g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 110 (Preparation of Cyan Dye Ink Composition 110) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 110 (100 g).
• Cyan dye (P-1) 1.69g Cyan dye (mixture of P-44-1 to P-44-4) 0.85 g Cyan dye (mixture of P-62-1 to P-62-4) 0.19 g Cyan dye (C-5) 1.27g Additive (A-4) 1.00 g Preservative 0.11g Glycerin 7.00g Ethylene urea 7.00g 1,5-pentanediol 7.00g 2-Pyrrolidone 5.00g Surfactant 0.50g
• Example 111 (Preparation of Cyan Dye Ink Composition 111) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 111 (100 g).
• Cyan dye (P-5) 1.07g Cyan dye (mixture of P-32-1 to P-32-4) 1.60 g Cyan dye (mixture of P-45-1 to P-45-4) 1.07 g Cyan dye (C-1) 0.26g Additive (A-4) 1.50 g EDTA (4 lithium salt) 0.05g
• Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 112 (Preparation of Cyan Dye Ink Composition 112) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 112 (100 g).
• Cyan dye (P-6) 1.07g Cyan dye (mixture of P-33-1 to P-33-4) 1.60 g Cyan dye (mixture of P-47-1 to P-47-4) 1.07 g Cyan dye (C-1) 0.26g Additive (A-4) 1.50 g EDTA (4 lithium salt) 0.05g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 113 (Preparation of Cyan Dye Ink Composition 113) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 113 (100 g).
• Cyan dye (P-7) 1.07g Cyan dye (mixture of P-34-1 to P-34-2) 1.60 g Cyan dye (mixture of P-59) 1.07 g Cyan dye (C-1) 0.26g Additive (A-4) 1.50 g EDTA (4 lithium salt) 0.05g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 114 (Preparation of Cyan Dye Ink Composition 114) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 114 (100 g).
• Cyan dye (P-22) 1.07g Cyan dye (mixture of P-39-1 to P-39-4) 1.60 g Cyan dye (mixture of P-49-1 to P-49-4) 1.07 g Cyan dye (C-16) 0.26g Additive (A-4) 1.50 g EDTA (4 lithium salt) 0.05g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 115 (Preparation of Cyan Dye Ink Composition 115) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 115 (100 g).
• Example 116 (Preparation of Cyan Dye Ink Composition 116) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 116 (100 g).
• Cyan dye (P-5) 1.52g Cyan dye (mixture of P-32-1 to P-32-4) 0.77 g Cyan dye (mixture of P-45-1 to P-45-4) 0.17 g Cyan dye (C-1) 1.14g Cyan dye (C-41) 0.40 g Additive (A-4) 1.00 g EDTA (4 lithium salt) 0.03g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 117 (Preparation of Cyan Dye Ink Composition 117) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 117 (100 g).
• Cyan dye (P-6) 1.52g Cyan dye (mixture of P-33-1 to P-33-4) 0.77 g Cyan dye (mixture of P-47-1 to P-47-4) 0.17 g Cyan dye (C-1) 1.14g Cyan dye (C-41) 0.40 g Additive (A-4) 1.00 g EDTA (4 lithium salt) 0.03g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 118 (Preparation of Cyan Dye Ink Composition 118) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 118 (100 g).
• Cyan dye (P-7) 1.52g Cyan dye (mixture of P-34-1 to P-34-2) 0.77 g Cyan dye (mixture of P-59) 0.17 g Cyan dye (C-1) 1.14g Cyan dye (C-41) 0.40 g Additive (A-4) 1.00 g EDTA (4 lithium salt) 0.03g
• Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Example 119 (Preparation of Cyan Dye Ink Composition 119) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 119 (100 g).
• Example 120 (Preparation of Cyan Dye Ink Composition 120) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 120 (100 g).
• Example 121 (Preparation of Cyan Dye Ink Composition 121) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 121 (100 g).
• Cyan dye (P-5) 1.07g Cyan dye (mixture of P-32-1 to P-32-4) 1.60 g Cyan dye (mixture of P-45-1 to P-45-4) 1.07 g Cyan dye (C-1) 0.26g Additive (A-4) 1.50 g EDTA (4 lithium salt) 0.02g Preservative 0.11g Glycerin 7.00g Ethylene urea 7.00g 1,5-pentanediol 7.00g 2-Pyrrolidone 5.00g Surfactant 0.50g
• Example 122 (Preparation of Cyan Dye Ink Composition 112) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 122 (100 g).
• Cyan dye (P-6) 1.07g Cyan dye (mixture of P-33-1 to P-33-4) 1.60 g Cyan dye (mixture of P-47-1 to P-47-4) 1.07 g Cyan dye (C-1) 0.26g Additive (A-4) 1.50 g EDTA (4 lithium salt) 0.02g Preservative 0.11g Glycerin 7.00g Ethylene urea 7.00g 1,5-pentanediol 7.00g 2-Pyrrolidone 5.00g Surfactant 0.50g
• Example 123 (Preparation of Cyan Dye Ink Composition 123) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 123 (100 g).
• Cyan dye (P-7) 1.07g Cyan dye (mixture of P-34-1 to P-34-2) 1.60 g Cyan dye (mixture of P-59) 1.07 g Cyan dye (C-1) 0.26g Additive (A-4) 1.50 g EDTA (4 lithium salt) 0.02g Preservative 0.11g Glycerin 7.00g Ethylene urea 7.00g 1,5-pentanediol 7.00g 2-Pyrrolidone 5.00g Surfactant 0.50g
• Example 124 (Preparation of Cyan Dye Ink Composition 124) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 124 (100 g).
• Cyan dye (P-22) 1.07g Cyan dye (mixture of P-39-1 to P-39-4) 1.60 g Cyan dye (mixture of P-49-1 to P-49-4) 1.07 g Cyan dye (C-16) 0.26g
• Additive (A-4) 1.50 g EDTA (4 lithium salt) 0.02g
• Example 125 (Preparation of Cyan Dye Ink Composition 125) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 125 (100 g).
• Example 126 (Preparation of Cyan Dye Ink Composition 126) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 126 (100 g).
• Example 127 (Preparation of Cyan Dye Ink Composition 127) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 127 (100 g).
• Example 128 (Preparation of Cyan Dye Ink Composition 128) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 128 (100 g).
• Cyan dye (P-7) 1.52g Cyan dye (mixture of P-34-1 to P-34-2) 0.77 g Cyan dye (mixture of P-59) 0.17 g Cyan dye (C-1) 1.14g Cyan dye (C-41) 0.40 g
• Additive (A-4) 1.00 g EDTA (4 lithium salt) 0.01g
• Example 129 (Preparation of Cyan Dye Ink Composition 129) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 129 (100 g).
• Example 130 (Preparation of Cyan Dye Ink Composition 130) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare a cyan dye ink composition 130 (100 g).
• Comparative Example 1 (Preparation of Comparative Cyan Dye Ink Composition 1) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare Comparative Cyan Dye Ink Composition 1 (100 g).
• Cyan dye (P-5) 1.69g Cyan dye (mixture of P-32-1 to P-32-4) 0.85 g Cyan dye (mixture of P-45-1 to P-45-4) 0.19 g Cyan dye (C-1) 1.27g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Comparative Example 2 (Preparation of Comparative Cyan Dye Ink Composition 2) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue. 10 g of deionized water from which the ink residue was recovered was added to the previously filtered 90 g mixture to prepare Comparative Cyan Dye Ink Composition 2 (100 g).
• Cyan dye (P-11) 1.69g Cyan dye (mixture of P-36-1 to P-36-4) 0.85 g Cyan dye (mixture of P-46-1 to P-46-4) 0.19 g Cyan dye (C-12) 1.27 g
• Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Comparative Example 3 (Preparation of Comparative Cyan Dye Ink Composition 3) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Comparative Cyan Dye Ink Composition 3 100 g.
• the dye concentration in the ink composition was quantitatively analyzed by performing the same operation as in Example 1.
• the dye solid content concentration was 4% by mass.
• Cyan dye (P-6) 1.69g Cyan dye (mixture of P-33-1 to P-33-4) 0.85 g Cyan dye (mixture of P-47-1 to P-47-4) 0.19 g Cyan dye (C-1) 1.27g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Comparative Example 4 (Preparation of Comparative Cyan Dye Ink Composition 4) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Comparative Cyan Dye Ink Composition 4 100 g.
• the dye concentration in the ink composition was quantitatively analyzed by performing the same operation as in Example 1.
• the dye solid content concentration was 4% by mass.
• Cyan dye (P-12) 1.69g Cyan dye (mixture of P-38-1 to P-38-4) 0.85 g Cyan dye (mixture of P-48-1 to P-48-4) 0.19 g Cyan dye (C-12) 1.27 g
• Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Comparative Example 5 (Preparation of Comparative Cyan Dye Ink Composition 5) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (P-7) 1.69g Cyan dye (mixture of P-34-1 to P-34-2) 0.85 g Cyan dye (P-59) 0.19g Cyan dye (C-1) 1.27g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Comparative Example 6 (Preparation of Comparative Cyan Dye Ink Composition 6) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (P-5) 1.07g Cyan dye (mixture of P-32-1 to P-32-4) 1.60 g Cyan dye (mixture of P-45-1 to P-45-4) 1.07 g Cyan dye (C-1) 0.26g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Comparative Example 7 (Preparation of Comparative Cyan Dye Ink Composition 7) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (P-11) 1.07g Cyan dye (mixture of P-36-1 to P-36-4) 1.60 g Cyan dye (mixture of P-46-1 to P-46-4) 1.07 g Cyan dye (C-12) 0.26g
• Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g
• Comparative Example 8 (Preparation of Comparative Cyan Dye Ink Composition 8) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (P-6) 1.07g Cyan dye (mixture of P-33-1 to P-33-4) 1.60 g Cyan dye (mixture of P-47-1 to P-47-4) 1.07 g Cyan dye (C-1) 0.26g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Comparative Example 9 (Preparation of Comparative Cyan Dye Ink Composition 9) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (P-12) 1.07g Cyan dye (mixture of P-38-1 to P-38-4) 1.60 g Cyan dye (mixture of P-48-1 to P-48-4) 1.07 g Cyan dye (C-12) 0.26g
• Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g
• Comparative Example 10 (Preparation of Comparative Cyan Dye Ink Composition 10) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (P-7) 1.07g Cyan dye (mixture of P-34-1 to P-34-2) 1.60 g Cyan dye (P-59) 1.07 g Cyan dye (C-1) 0.26g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Cyan dye (P-5) 2.11g Cyan dye (mixture of P-32-1 to P-32-4) 1.05 g Cyan dye (mixture of P-45-1 to P-45-4) 0.24 g Cyan dye (C-1) 1.59g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Comparative Example 12 (Preparation of Comparative Cyan Dye Ink Composition 12) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (P-11) 2.11g Cyan dye (mixture of P-36-1 to P-36-4) 1.05 g Cyan dye (mixture of P-46-1 to P-46-4) 0.24 g Cyan dye (C-12) 1.59g
• Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Cyan dye (P-6) 2.11g Cyan dye (mixture of P-33-1 to P-33-4) 1.05 g Cyan dye (mixture of P-47-1 to P-47-4) 0.24 g Cyan dye (C-1) 1.59g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Comparative Example 14 (Preparation of Comparative Cyan Dye Ink Composition 14) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (P-12) 2.11g Cyan dye (mixture of P-38-1 to P-38-4) 1.05 g Cyan dye (mixture of P-48-1 to P-48-4) 0.24 g Cyan dye (C-12) 1.59g
• Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Comparative Example 15 (Preparation of Comparative Cyan Dye Ink Composition 15) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (P-7) 2.11g Cyan dye (mixture of P-34-1 to P-34-2) 1.05 g Cyan dye (P-59) 0.24g Cyan dye (C-1) 1.59g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Comparative Example 16 (Preparation of Comparative Cyan Dye Ink Composition 16) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (P-5) 1.27g Cyan dye (mixture of P-32-1 to P-32-4) 0.64 g Cyan dye (mixture of P-45-1 to P-45-4) 0.13 g Cyan dye (C-1) 0.96 g
• Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g
• Comparative Example 17 (Preparation of Comparative Cyan Dye Ink Composition 17) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (P-11) 1.27g Cyan dye (mixture of P-36-1 to P-36-4) 0.64 g Cyan dye (mixture of P-46-1 to P-46-4) 0.13 g Cyan dye (C-12) 0.96g
• Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g
• Comparative Example 18 (Preparation of Comparative Cyan Dye Ink Composition 18) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (P-6) 1.27g Cyan dye (mixture of P-33-1 to P-33-4) 0.64 g Cyan dye (mixture of P-47-1 to P-47-4) 0.13 g Cyan dye (C-1) 0.96 g
• Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g
• Comparative Example 19 (Preparation of Comparative Cyan Dye Ink Composition 19) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (P-12) 1.27g Cyan dye (mixture of P-38-1 to P-38-4) 0.64 g Cyan dye (mixture of P-48-1 to P-48-4) 0.13 g Cyan dye (C-12) 0.96g
• Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g
• Comparative Example 20 (Preparation of Comparative Cyan Dye Ink Composition 20) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (P-7) 1.27g Cyan dye (mixture of P-34-1 to P-34-2) 0.64 g Cyan dye (P-59) 0.13g Cyan dye (C-1) 0.96 g
• Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g
• Surfactant 1.00g
• Comparative Example 21 (Preparation of Comparative Cyan Dye Ink Composition 21) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (P-18) 1.69g Cyan dye (mixture of P-41-1 to P-41-1) 0.85 g Cyan dye (mixture of P-53-1 to P-53-4) 0.19 g Cyan dye (C-10) 1.27g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Cyan dye (P-19) 1.69g Cyan dye (mixture of P-42-1 to P-42-4) 0.85 g Cyan dye (mixture of P-55-1 to P-55-4) 0.19 g Cyan dye (C-10) 1.27g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Comparative Example 23 (Preparation of Comparative Cyan Dye Ink Composition 23) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (P-20) 1.69g Cyan dye (mixture of P-43-1 to P-43-4) 0.85 g Cyan dye (mixture of P-57-1 to P-57-4) 0.19 g Cyan dye (C-11) 1.27 g
• Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Comparative Example 24 (Preparation of Comparative Cyan Dye Ink Composition 24) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (P-22) 1.69g Cyan dye (mixture of P-39-1 to P-39-4) 0.85 g Cyan dye (mixture of P-49-1 to P-49-4) 0.19 g Cyan dye (C-16) 1.27g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Comparative Example 25 (Preparation of Comparative Cyan Dye Ink Composition 25) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (P-23) 1.69g Cyan dye (mixture of P-40-1 to P-40-4) 0.85 g Cyan dye (mixture of P-51-1 to P-51-4) 0.19 g Cyan dye (C-16) 1.27g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Comparative Example 26 (Preparation of Comparative Cyan Dye Ink Composition 26) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Comparative Example 27 (Preparation of Comparative Cyan Dye Ink Composition 27) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Comparative Example 28 (Preparation of Comparative Cyan Dye Ink Composition 28) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Comparative Example 29 (Preparation of Comparative Cyan Dye Ink Composition 29) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (CI Acid Blue9) 3.60g Cyan dye (C-41) 0.40 g Additive (A-4) 1.00 g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Comparative Example 30 (Preparation of Comparative Cyan Dye Ink Composition 30) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (CI Acid Blue9) 3.60g Cyan dye (C-12) 0.20 g Cyan dye (C-42) 0.20g Additive (A-3) 1.00 g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Comparative Example 31 (Preparation of Comparative Cyan Dye Ink Composition 31) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Comparative Example 32 (Preparation of Comparative Cyan Dye Ink Composition 32) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Comparative Example 33 (Preparation of Comparative Cyan Dye Ink Composition 33) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan Dye (CI Direct Blue 199) 3.60g Cyan dye (C-42) 0.40g Additive (A-3) 1.00 g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Comparative Example 34 (Preparation of Comparative Cyan Dye Ink Composition 34) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan Dye (CI Direct Blue 199) 3.60g Cyan dye (C-41) 0.40 g Additive (A-4) 1.00 g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Comparative Example 35 (Preparation of Comparative Cyan Dye Ink Composition 35) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan Dye (CI Direct Blue 199) 3.60g Cyan dye (C-12) 0.20 g Cyan dye (C-42) 0.20g Additive (A-3) 1.00 g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Comparative Example 36 (Preparation of Comparative Cyan Dye Ink Composition 36) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Comparative Example 37 (Preparation of Comparative Cyan Dye Ink Composition 37) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (CI Acid Blue9) 2.00g Cyan Dye (CI Director Blue199) 2.00g Additive (A-3) 1.00 g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Comparative Example 38 (Preparation of Comparative Cyan Dye Ink Composition 38) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (CI Acid Blue9) 1.80g Cyan Dye (CI Director Blue199) 1.80g Cyan dye (C-42) 0.40g Additive (A-3) 1.00 g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Cyan dye (CI Acid Blue9) 1.80g Cyan Dye (CI Director Blue199) 1.80g Cyan dye (C-12) 0.20 g Cyan dye (C-42) 0.20g Additive (A-3) 1.00 g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Comparative Example 40 (Preparation of Comparative Cyan Dye Ink Composition 40) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (CI Acid Blue9) 1.80g Cyan Dye (CI Director Blue199) 1.80g Cyan dye (C-1) 0.20 g Cyan dye (C-41) 0.20 g Additive (A-4) 1.00 g Preservative 0.11g Glycerin 9.70g Triethylene glycol 3.40g Triethylene glycol monobutyl ether 9.90 g 2-Pyrrolidone 2.50 g 1,2-hexanediol 1.30g Propylene glycol 0.12g Surfactant 1.00g
• Cyan dye (P-5) 1.69g Cyan dye (mixture of P-32-1 to P-32-4) 0.85 g Cyan dye (mixture of P-45-1 to P-45-4) 0.19 g Cyan dye (C-1) 1.27g Preservative 0.11g Glycerin 7.00g Ethylene urea 7.00g 1,5-pentanediol 7.00g 2-Pyrrolidone 5.00g Surfactant 0.50g
• Comparative Example 42 (Preparation of Comparative Cyan Dye Ink Composition 42) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (P-11) 1.69g Cyan dye (mixture of P-36-1 to P-36-4) 0.85 g Cyan dye (mixture of P-46-1 to P-46-4) 0.19 g Cyan dye (C-12) 1.27 g Preservative 0.11g Glycerin 7.00g Ethylene urea 7.00g 1,5-pentanediol 7.00g 2-Pyrrolidone 5.00g Surfactant 0.50g
• Comparative Example 43 (Preparation of Comparative Cyan Dye Ink Composition 43) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (P-6) 1.69g Cyan dye (mixture of P-33-1 to P-33-4) 0.85 g Cyan dye (mixture of P-47-1 to P-47-4) 0.19 g Cyan dye (C-1) 1.27g Preservative 0.11g Glycerin 7.00g Ethylene urea 7.00g 1,5-pentanediol 7.00g 2-Pyrrolidone 5.00g Surfactant 0.50g
• Comparative Example 44 (Preparation of Comparative Cyan Dye Ink Composition 44) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (P-12) 1.69g Cyan dye (mixture of P-38-1 to P-38-4) 0.85 g Cyan dye (mixture of P-48-1 to P-48-4) 0.19 g Cyan dye (C-12) 1.27 g Preservative 0.11g Glycerin 7.00g Ethylene urea 7.00g 1,5-pentanediol 7.00g 2-Pyrrolidone 5.00g Surfactant 0.50g
• Comparative Example 45 (Preparation of Comparative Cyan Dye Ink Composition 45) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (P-7) 1.69g Cyan dye (mixture of P-34-1 to P-34-2) 0.85 g Cyan dye (P-59) 0.19g Cyan dye (C-1) 1.27g Preservative 0.11g Glycerin 7.00g Ethylene urea 7.00g 1,5-pentanediol 7.00g 2-Pyrrolidone 5.00g Surfactant 0.50g
• Comparative Example 46 (Preparation of Comparative Cyan Dye Ink Composition 46) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (P-5) 1.07g Cyan dye (mixture of P-32-1 to P-32-4) 1.60 g Cyan dye (mixture of P-45-1 to P-45-4) 1.07 g Cyan dye (C-1) 0.26g Preservative 0.11g Glycerin 7.00g Ethylene urea 7.00g 1,5-pentanediol 7.00g 2-Pyrrolidone 5.00g Surfactant 0.50g
• Comparative Example 47 (Preparation of Comparative Cyan Dye Ink Composition 47) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (P-11) 1.07g Cyan dye (mixture of P-36-1 to P-36-4) 1.60 g Cyan dye (mixture of P-46-1 to P-46-4) 1.07 g Cyan dye (C-12) 0.26g
• Comparative Example 48 (Preparation of Comparative Cyan Dye Ink Composition 48) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (P-6) 1.07g Cyan dye (mixture of P-33-1 to P-33-4) 1.60 g Cyan dye (mixture of P-47-1 to P-47-4) 1.07 g Cyan dye (C-1) 0.26g Preservative 0.11g Glycerin 7.00g Ethylene urea 7.00g 1,5-pentanediol 7.00g 2-Pyrrolidone 5.00g Surfactant 0.50g
• Comparative Example 49 (Preparation of Comparative Cyan Dye Ink Composition 49) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (P-12) 1.07g Cyan dye (mixture of P-38-1 to P-38-4) 1.60 g Cyan dye (mixture of P-48-1 to P-48-4) 1.07 g Cyan dye (C-12) 0.26g
• Comparative Example 50 (Preparation of Comparative Cyan Dye Ink Composition 50) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (P-7) 1.07g Cyan dye (mixture of P-34-1 to P-34-2) 1.60 g Cyan dye (P-59) 1.07 g Cyan dye (C-1) 0.26g Preservative 0.11g Glycerin 7.00g Ethylene urea 7.00g 1,5-pentanediol 7.00g 2-Pyrrolidone 5.00g Surfactant 0.50g
• Comparative Example 51 (Preparation of Comparative Cyan Dye Ink Composition 51) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (P-5) 2.11g Cyan dye (mixture of P-32-1 to P-32-4) 1.05 g Cyan dye (mixture of P-45-1 to P-45-4) 0.24 g Cyan dye (C-1) 1.59g Preservative 0.11g Glycerin 7.00g Ethylene urea 7.00g 1,5-pentanediol 7.00g 2-Pyrrolidone 5.00g Surfactant 0.50g
• Comparative Example 52 (Preparation of Comparative Cyan Dye Ink Composition 52) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (P-11) 2.11g Cyan dye (mixture of P-36-1 to P-36-4) 1.05 g Cyan dye (mixture of P-46-1 to P-46-4) 0.24 g Cyan dye (C-12) 1.59g
• Preservative 0.11g Glycerin 7.00g Ethylene urea 7.00g 1,5-pentanediol 7.00g 2-Pyrrolidone 5.00g
• Comparative Example 53 (Preparation of Comparative Cyan Dye Ink Composition 53) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (P-6) 2.11g Cyan dye (mixture of P-33-1 to P-33-4) 1.05 g Cyan dye (mixture of P-47-1 to P-47-4) 0.24 g Cyan dye (C-1) 1.59g Preservative 0.11g Glycerin 7.00g Ethylene urea 7.00g 1,5-pentanediol 7.00g 2-Pyrrolidone 5.00g Surfactant 0.50g
• Comparative Example 54 (Preparation of Comparative Cyan Dye Ink Composition 54) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (P-12) 2.11g Cyan dye (mixture of P-38-1 to P-38-4) 1.05 g Cyan dye (mixture of P-48-1 to P-48-4) 0.24 g Cyan dye (C-12) 1.59g
• Comparative Example 55 (Preparation of Comparative Cyan Dye Ink Composition 55) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (P-7) 2.11g Cyan dye (mixture of P-34-1 to P-34-2) 1.05 g Cyan dye (P-59) 0.24g Cyan dye (C-1) 1.59g Preservative 0.11g Glycerin 7.00g Ethylene urea 7.00g 1,5-pentanediol 7.00g 2-Pyrrolidone 5.00g Surfactant 0.50g
• Comparative Example 56 (Preparation of Comparative Cyan Dye Ink Composition 56) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (P-5) 1.27g Cyan dye (mixture of P-32-1 to P-32-4) 0.64 g Cyan dye (mixture of P-45-1 to P-45-4) 0.13 g Cyan dye (C-1) 0.96 g Preservative 0.11g Glycerin 7.00g Ethylene urea 7.00g 1,5-pentanediol 7.00g 2-Pyrrolidone 5.00g Surfactant 0.50g
• Comparative Example 57 (Preparation of Comparative Cyan Dye Ink Composition 57) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (P-11) 1.27g Cyan dye (mixture of P-36-1 to P-36-4) 0.64 g Cyan dye (mixture of P-46-1 to P-46-4) 0.13 g Cyan dye (C-12) 0.96g
• Comparative Example 58 (Preparation of Comparative Cyan Dye Ink Composition 58) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (P-6) 1.27g Cyan dye (mixture of P-33-1 to P-33-4) 0.64 g Cyan dye (mixture of P-47-1 to P-47-4) 0.13 g Cyan dye (C-1) 0.96 g Preservative 0.11g Glycerin 7.00g Ethylene urea 7.00g 1,5-pentanediol 7.00g 2-Pyrrolidone 5.00g Surfactant 0.50g
• Comparative Example 59 (Preparation of Comparative Cyan Dye Ink Composition 59) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (P-12) 1.27g Cyan dye (mixture of P-38-1 to P-38-4) 0.64 g Cyan dye (mixture of P-48-1 to P-48-4) 0.13 g Cyan dye (C-12) 0.96g Preservative 0.11g Glycerin 7.00g Ethylene urea 7.00g 1,5-pentanediol 7.00g 2-Pyrrolidone 5.00g Surfactant 0.50g
• Comparative Example 60 (Preparation of Comparative Cyan Dye Ink Composition 60) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (P-7) 1.27g Cyan dye (mixture of P-34-1 to P-34-2) 0.64 g Cyan dye (P-59) 0.13g Cyan dye (C-1) 0.96 g Preservative 0.11g Glycerin 7.00g Ethylene urea 7.00g 1,5-pentanediol 7.00g 2-Pyrrolidone 5.00g Surfactant 0.50g
• Comparative Example 61 (Preparation of Comparative Cyan Dye Ink Composition 61) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (P-18) 1.69g Cyan dye (mixture of P-41-1 to P-41-1) 0.85 g Cyan dye (mixture of P-53-1 to P-53-4) 0.19 g Cyan dye (C-10) 1.27g Preservative 0.11g Glycerin 7.00g Ethylene urea 7.00g 1,5-pentanediol 7.00g 2-Pyrrolidone 5.00g Surfactant 0.50g
• Comparative Example 62 (Preparation of Comparative Cyan Dye Ink Composition 62) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (P-19) 1.69g Cyan dye (mixture of P-42-1 to P-42-4) 0.85 g Cyan dye (mixture of P-55-1 to P-55-4) 0.19 g Cyan dye (C-10) 1.27g Preservative 0.11g Glycerin 7.00g Ethylene urea 7.00g 1,5-pentanediol 7.00g 2-Pyrrolidone 5.00g Surfactant 0.50g
• Comparative Example 63 (Preparation of Comparative Cyan Dye Ink Composition 63) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (P-20) 1.69g Cyan dye (mixture of P-43-1 to P-43-4) 0.85 g Cyan dye (mixture of P-57-1 to P-57-4) 0.19 g Cyan dye (C-11) 1.27 g
• Comparative Example 64 (Preparation of Comparative Cyan Dye Ink Composition 64) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (P-22) 1.69g Cyan dye (mixture of P-39-1 to P-39-4) 0.85 g Cyan dye (mixture of P-49-1 to P-49-4) 0.19 g Cyan dye (C-16) 1.27g Preservative 0.11g Glycerin 7.00g Ethylene urea 7.00g 1,5-pentanediol 7.00g 2-Pyrrolidone 5.00g Surfactant 0.50g
• Comparative Example 65 (Preparation of Comparative Cyan Dye Ink Composition 65) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (P-23) 1.69g Cyan dye (mixture of P-40-1 to P-40-4) 0.85 g Cyan dye (mixture of P-51-1 to P-51-4) 0.19 g Cyan dye (C-16) 1.27g Preservative 0.11g Glycerin 7.00g Ethylene urea 7.00g 1,5-pentanediol 7.00g 2-Pyrrolidone 5.00g Surfactant 0.50g
• Comparative Example 66 (Preparation of Comparative Cyan Dye Ink Composition 66) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Comparative Example 67 (Preparation of Comparative Cyan Dye Ink Composition 67) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Comparative Example 68 (Preparation of Comparative Cyan Dye Ink Composition 68) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Comparative Example 69 (Preparation of Comparative Cyan Dye Ink Composition 69) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Comparative Example 70 (Preparation of Comparative Cyan Dye Ink Composition 70) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Comparative Example 71 (Preparation of Comparative Cyan Dye Ink Composition 71) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Comparative Example 72 (Preparation of Comparative Cyan Dye Ink Composition 72) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Comparative Example 73 (Preparation of Comparative Cyan Dye Ink Composition 73) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Comparative Example 74 (Preparation of Comparative Cyan Dye Ink Composition 74) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Comparative Example 75 (Preparation of Comparative Cyan Dye Ink Composition 75) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Comparative Example 76 (Preparation of Comparative Cyan Dye Ink Composition 76) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Comparative Example 77 (Preparation of Comparative Cyan Dye Ink Composition 77) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Comparative Example 78 (Preparation of Comparative Cyan Dye Ink Composition 78) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Comparative Example 79 (Preparation of Comparative Cyan Dye Ink Composition 78) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L aqueous sodium hydroxide solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (CI Acid Blue9) 1.80g Cyan Dye (CI Director Blue199) 1.80g Cyan dye (C-12) 0.20 g Cyan dye (C-42) 0.20g Additive (A-3) 1.00 g Preservative 0.11g Glycerin 7.00g Ethylene urea 7.00g 1,5-pentanediol 7.00g 2-Pyrrolidone 5.00g Surfactant 0.50g
• Comparative Example 80 (Preparation of Comparative Cyan Dye Ink Composition 80) Deionized water was added to a mixture containing the following components in the following addition amounts to make 90 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Then, the pH was adjusted to 9.0 with a 10 mol / L lithium hydroxide aqueous solution, filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m, and then the filter was washed with 10 g of deionized water to recover the ink residue.
• Cyan dye (CI Acid Blue9) 1.80g Cyan Dye (CI Director Blue199) 1.80g Cyan dye (C-1) 0.20 g Cyan dye (C-41) 0.20 g Additive (A-4) 1.00 g Preservative 0.11g Glycerin 7.00g Ethylene urea 7.00g 1,5-pentanediol 7.00g 2-Pyrrolidone 5.00g Surfactant 0.50g
• Each of the cyan dye ink compositions of Examples 71 to 101, 105 to 107, 110, 121 to 130, and Comparative Examples 41 to 80 is loaded into an ink cartridge, and an inkjet printer (manufactured by Canon Inc .; PIXUS Pro9000MkII) is used exclusively for inkjet. It was evaluated using images recorded on paper (manufactured by Canon Inc .; photo glossy paper PT-201) and plain paper (Xerox P paper: manufactured by FUJI Xerox).
• ⁇ Print density (color development)> A solid coating image (printed image at an applied voltage of 100%) was recorded using each cyan dye ink composition with the combination of the above-mentioned inkjet printer and recording paper.
• the print density of the created solid-painted image was measured using a reflection densitometer (trade name X-Rite310TR, manufactured by X-Rite Co., Ltd.), and the single-color cyan image was the print density (Optical) when the red filter was used. Density) was evaluated on the following four stages.
• ⁇ Ozone resistance> 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 ⁇ 0.1 ppm (parts per million), room temperature (23 ° C; 50% relative humidity).
• the paper on which the image was formed was left in a box set in a dark place for 5 days, and the image density after being left under ozone gas was measured using a reflection densitometer (trade name X-Rite 310TR, manufactured by Xrite).
• the dye residual ratio was calculated and evaluated from the initial image concentration Ci and the image concentration Cf2 after being left under ozone gas. The dye residual ratio was measured using an image portion having an initial image density of 1.0 ⁇ 0.2.
• the ozone gas concentration in the box was set using an ozone gas monitor (model: OZG-EM-01) manufactured by APPLICS.
• the red filter used for measuring the cyan image density was used.
• the dye residual ratio was calculated from the following formula, and the ozone resistance was evaluated according to the following criteria.
• Dye residual rate (%) (Cf2 / Ci) x 100 AA: When the dye residual rate is 85% or more and less than 95% A: When the dye residual rate is 80% or more and less than 85% B: When the dye residual rate is 75% or more and less than 80% C: When the dye residual rate is 70% When it is more than 75% D: When the dye residual rate is less than 70%
• ⁇ Light resistance> After measuring the image density Ci immediately after recording, the image is irradiated with xenone light (100 klux, 23 ° C., relative humidity 50%; SC37 370 nm or less with a cut filter) for 28 days using a weather meter (Atlas C.165). After that, the image density Cf1 was measured again, and the dye residual rate was calculated and evaluated from the image density before and after the xenon light irradiation. The image density was measured using a reflection densitometer (trade name: X-Rite 310TR, manufactured by Xrite). The dye residual ratio was measured using an image portion having an initial image density of 1.0 ⁇ 0.2. The red filter used for measuring the cyan image density was used.
• the dye residual ratio was calculated from the following formula, and the light resistance was evaluated according to the following criteria.
• Dye residual rate (%) (Cf1 / Ci) x 100 A: When the dye residual rate is 90% or more and less than 95% B: When the dye residual rate is 80% or more and less than 90% C: When the dye residual rate is 70% or more and less than 80% D: When the dye residual rate is 70% If less than
• the cyan dye ink compositions prepared in Examples 1 to 70, 102 to 104, 108 to 109, and 111 to 120 were used in an inkjet recording device (trade name: PM-700C, manufactured by Seiko Epson Corporation). Fill the ink cartridge for use, set this cartridge in the inkjet recording device, check the ink ejection from all nozzles, and then 100 sheets of A4 paper (inkjet paper, photo paper manufactured by Seiko Epson Corporation ⁇ glossy >) was output and evaluated according to the following criteria.
• the cyan dye ink compositions prepared in Examples 71 to 101, 105 to 107, 110, 121 to 130 are filled in an ink cartridge for an inkjet recording device (trade name: PIXUS Pro9000MkII, manufactured by Canon Inc.). After setting the cartridge in the inkjet recording device and checking the ejection of ink from all the nozzles, output it to 100 sheets of A4 paper (inkjet paper, manufactured by Canon Inc .; photo glossy paper PT-201), and output as follows. Evaluated by criteria. A: There is almost no print distortion from the start to the end of printing B: A small number of outputs with print distortion occur C: Many outputs with print distortion occur D: There is print distortion from the beginning to the end of printing
• the ink ejection stability test was performed immediately after the dye ink composition was prepared and after storage in an ink cartridge under the conditions of 40 ° C. and 80% relative humidity for 4 weeks.
• the results when the dye ink composition immediately after preparation is used are described in the column of "immediately after ink preparation”.
• the results of storage in an ink cartridge under the conditions of 40 ° C. and 80% relative humidity for 4 weeks are described in the column of "4 weeks after compulsory test".
• ⁇ Storage stability> The cyan dye ink compositions prepared in Examples 1 to 130 were evaluated for ink storage stability as a compulsory test after being stored at 60 ° C. for 4 weeks and after being stored at 60 ° C. for 10 weeks. did. Those that maintain the same performance as the dye ink composition immediately after preparation are A, and those whose performance is degraded even by one of the evaluation items (print density, light resistance, ozone resistance, and ejection stability) after the compulsory test. It was rated as B and evaluated on a two-point scale.
• the cyan dye ink composition of the example of the present invention produces an image having excellent printing density (color development) and durability (light resistance and ozone resistance) on plain paper and inkjet paper. It turned out to be a dye ink composition that can be formed. Further, the cyan dye ink composition of the present invention is excellent in storage stability during long-term storage, printing quality of ink after long-term storage, and ejection stability. Therefore, the dye ink composition of the example of the present invention was excellent in printing density (color development property) on plain paper for document use. Further, it has a high level of durability (light resistance and ozone resistance of an inkjet photographic paper) on an inkjet paper for photographic use, and is superior to conventional techniques in terms of long-term storage stability.
• a dye ink composition capable of forming an image having excellent printing density (particularly, color development on plain paper) and excellent ozone resistance and light resistance, a dye ink for inkjet recording, and a dye ink for inkjet recording.
• An inkjet recording method can be provided.

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