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
  • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B33/00—Disazo and polyazo dyes of the types A->K<-B, A->B->K<-C, or the like, prepared by diazotising and coupling
  • C09B33/18—Trisazo or higher polyazo dyes
  • C09B33/28—Tetrazo dyes of the type A->B->K<-C<-D
• • 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
  • C09B35/00—Disazo and polyazo dyes of the type A<-D->B prepared by diazotising and coupling
  • C09B35/02—Disazo dyes
  • C09B35/039—Disazo dyes characterised by the tetrazo component
  • C09B35/34—Disazo dyes characterised by the tetrazo component the tetrazo component being heterocyclic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B47/00—Porphines; Azaporphines
  • C09B47/04—Phthalocyanines abbreviation: Pc
  • C09B47/08—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex
  • C09B47/20—Obtaining compounds having sulfur atoms directly bound to the phthalocyanine skeleton
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B5/00—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings
  • C09B5/02—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings the heterocyclic ring being only condensed in peri position
  • C09B5/14—Benz-azabenzanthrones (anthrapyridones)
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
  • C09B67/0083—Solutions of dyes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/30—Inkjet printing inks
  • C09D11/32—Inkjet printing inks characterised by colouring agents
  • C09D11/328—Inkjet printing inks characterised by colouring agents characterised by dyes

Definitions

• the present invention relates to an aqueous additive solution for an ink composition, an aqueous solution of a colorant for an ink composition, an ink composition, an ink composition for inkjet recording, and an inkjet recording method.
• the ink jet recording method is rapidly spreading and further developing because of its low material cost, high speed recording, low noise during recording, and ease of color recording.
• Compositions containing various colorants (pigments) have been proposed as ink compositions used in ink jet recording methods.
• compounds (additives) to be added to the ink composition are also being investigated.
• Patent Documents 1 to 3 describe compounds with high planarity as additives that can be used in dye-containing ink compositions.
• inkjet printers equipped with large-capacity ink tanks with a capacity of 50 mL or more have been developed. It is said to be superior in However, in a large-capacity ink tank, the ink composition remains in the ink tank for a long period of time, so the ink composition is required to have an unprecedented level of storage stability. In addition, an aqueous additive solution used for preparing an ink composition is also required to have storage stability.
• Patent document 1 does not consider the above viewpoint.
• Patent Documents 2 and 3 discuss the storage stability of ink compositions, but there is room for further improvement. Moreover, the storage stability of the additive aqueous solution has not been investigated.
• the pH value of the additive aqueous solution and the colorant aqueous solution used in the preparation of the ink composition becomes high (e.g., the pH value becomes higher than 9.0)
• high pH values of the aqueous additive solution, the aqueous colorant solution, and the ink composition may result in decomposition of the colorant and additives.
• the pH value of the additive aqueous solution and the coloring agent aqueous solution becomes low (for example, the pH value becomes lower than 6.0), the risk of precipitation of the coloring agent (eg, acid dye) and additives increases.
• the pH value of the ink composition becomes lower (eg, pH value less than 6.0), the risk of corrosion of the ink head of the inkjet printer increases.
• the risk of precipitation of coloring agents (eg, acid dyes) and additives increases, as with the additive aqueous solution and the coloring agent aqueous solution. Therefore, fluctuations in the pH value are linked to the optimized physical properties of the liquid (solubility stability, absorbance, viscosity, surface tension, etc.), and there is concern that it may affect the delicate characteristics of the ink head (for example, Ink ejection stability (clogging) and continuous ejection stability (reliability) may be reduced).
• the object of the present invention is to have excellent storage stability (excellent antiseptic properties, less precipitation of insoluble matter when stored for a long period of time, less change in absorbance, viscosity, and surface tension, and less change in pH value. ), an aqueous additive solution for an ink composition, an aqueous colorant solution and an ink composition for an ink composition, an ink composition for inkjet recording containing the ink composition, and an inkjet recording method using the ink composition for inkjet recording. to do.
• T 1 , T 2 and T 3 are each independently *-NH-(CH 2 ) n -Rt, *-NH-(CH 2 ) n -OH, *-N- ⁇ (CH 2 ) n —OH ⁇ 2 , *—NH—CH 2 CH(OH)CH 2 —Rt, *—OM, a halogen atom, or a substituted or unsubstituted arylamino group.
• T 1 , T 2 and T 3 is *-NH-(CH 2 ) n -Rt, *-NH-(CH 2 ) n -OH, *-N- ⁇ (CH 2 ) n —OH ⁇ 2 or *—NH—CH 2 CH(OH)CH 2 —Rt.
• * represents a binding site to the triazine ring
• n represents an integer from 1 to 5
• Rt represents CO 2 M, SO 3 M, or PO(OM) 2 .
• M represents a hydrogen atom or a counter cation. When there are multiple n's, the multiple n's may be the same or different. When there are multiple M's, the multiple M's may be the same or different.
• Ar 20 represents a benzene ring or a naphthalene ring.
• R 21 to R 28 each independently represent a hydrogen atom or a substituent.
• R 21 and R 22 may combine to form a ring.
• R 23 and R 24 may combine to form a ring.
• R 25 and R 26 may combine to form a ring.
• R 27 and R 28 may combine to form a ring.
• R29 represents a substituent.
• k represents an integer of 0-4.
• Ar 20 represents a naphthalene ring
• k represents an integer of 0-6.
• the multiple R 29 may be the same or different.
• the compound represented by general formula (II) has at least one hydrophilic group.
• M in the compounds of the compound group (a) represents a hydrogen atom or a counter cation.
• the multiple M's may be the same or different.
• the additive aqueous solution for an ink composition according to any one of .
• ⁇ 5> ⁇ 1> to ⁇ 4> wherein the content of the compound represented by the general formula (A) is 0.01 to 1.0% by mass based on the total mass of the additive aqueous solution for the ink composition.
• the additive aqueous solution for an ink composition according to any one of . ⁇ 6> The additive aqueous solution for an ink composition according to any one of ⁇ 1> to ⁇ 5>, further comprising a chelating agent.
• ⁇ 8> The additive aqueous solution for an ink composition according to any one of ⁇ 1> to ⁇ 7>, further comprising a preservative.
• ⁇ 9> The additive aqueous solution for an ink composition according to ⁇ 8>, wherein the content of the preservative is 0.01 to 1.0% by mass based on the total mass of the additive aqueous solution for the ink composition.
• ⁇ 10> The additive aqueous solution for an ink composition according to any one of ⁇ 1> to ⁇ 9>, further containing a buffering agent.
• ⁇ 11> The aqueous additive solution for an ink composition according to any one of ⁇ 1> to ⁇ 10>, which has a pH value of 6.5 to 9.0 at 25°C.
• T 1 , T 2 and T 3 are each independently *-NH-(CH 2 ) n -Rt, *-NH-(CH 2 ) n -OH, *-N- ⁇ (CH 2 ) n —OH ⁇ 2 , *—NH—CH 2 CH(OH)CH 2 —Rt, *—OM, a halogen atom, or a substituted or unsubstituted arylamino group.
• T 1 , T 2 and T 3 is *-NH-(CH 2 ) n -Rt, *-NH-(CH 2 ) n -OH, *-N- ⁇ (CH 2 ) n —OH ⁇ 2 or *—NH—CH 2 CH(OH)CH 2 —Rt.
• * represents a binding site to the triazine ring
• n represents an integer from 1 to 5
• Rt represents CO 2 M, SO 3 M, or PO(OM) 2 .
• M represents a hydrogen atom or a counter cation. When there are multiple n's, the multiple n's may be the same or different. When there are multiple M's, the multiple M's may be the same or different.
• Ar 20 represents a benzene ring or a naphthalene ring.
• R 21 to R 28 each independently represent a hydrogen atom or a substituent.
• R 21 and R 22 may combine to form a ring.
• R 23 and R 24 may combine to form a ring.
• R 25 and R 26 may combine to form a ring.
• R 27 and R 28 may combine to form a ring.
• R29 represents a substituent.
• k represents an integer of 0-4.
• Ar 20 represents a naphthalene ring
• k represents an integer of 0-6.
• the multiple R 29 may be the same or different.
• the compound represented by general formula (II) has at least one hydrophilic group.
• M in the compounds of the compound group (a) represents a hydrogen atom or a counter cation.
• the multiple M's may be the same or different.
• ⁇ 16> ⁇ 12> to ⁇ 15> wherein the content of the compound represented by the general formula (II) is 0.5 to 8.0% by mass based on the total mass of the aqueous colorant solution for the ink composition.
• ⁇ 18> The aqueous colorant solution for an ink composition according to any one of ⁇ 12> to ⁇ 17>, further comprising a chelating agent.
• ⁇ 19> The aqueous colorant solution for an ink composition according to ⁇ 18>, wherein the content of the chelating agent is 0.001 to 1.0% by mass based on the total mass of the aqueous additive solution for the ink composition.
• ⁇ 20> The aqueous colorant solution for an ink composition according to any one of ⁇ 12> to ⁇ 19>, further comprising a preservative.
• ⁇ 21> The aqueous colorant solution for an ink composition according to ⁇ 20>, wherein the content of the preservative is 0.01 to 1.0% by mass based on the total mass of the aqueous additive solution for the ink composition.
• ⁇ 22> The aqueous colorant solution for an ink composition according to any one of ⁇ 12> to ⁇ 21>, further comprising a buffering agent.
• ⁇ 23> The aqueous colorant solution for an ink composition according to any one of ⁇ 12> to ⁇ 22>, which has a pH value of 6.5 to 9.0 at 25°C.
• T 1 , T 2 and T 3 are each independently *-NH-(CH 2 ) n -Rt, *-NH-(CH 2 ) n -OH, *-N- ⁇ (CH 2 ) n —OH ⁇ 2 , *—NH—CH 2 CH(OH)CH 2 —Rt, *—OM, a halogen atom, or a substituted or unsubstituted arylamino group.
• T 1 , T 2 and T 3 is *-NH-(CH 2 ) n -Rt, *-NH-(CH 2 ) n -OH, *-N- ⁇ (CH 2 ) n —OH ⁇ 2 or *—NH—CH 2 CH(OH)CH 2 —Rt.
• * represents a binding site to the triazine ring
• n represents an integer from 1 to 5
• Rt represents CO 2 M, SO 3 M, or PO(OM) 2 .
• M represents a hydrogen atom or a counter cation. When there are multiple n's, the multiple n's may be the same or different. When there are multiple M's, the multiple M's may be the same or different.
• Ar 20 represents a benzene ring or a naphthalene ring.
• R 21 to R 28 each independently represent a hydrogen atom or a substituent.
• R 21 and R 22 may combine to form a ring.
• R 23 and R 24 may combine to form a ring.
• R 25 and R 26 may combine to form a ring.
• R 27 and R 28 may combine to form a ring.
• R29 represents a substituent.
• k represents an integer of 0-4.
• Ar 20 represents a naphthalene ring
• k represents an integer of 0-6.
• the multiple R 29 may be the same or different.
• the compound represented by general formula (II) has at least one hydrophilic group.
• M in the compounds of the compound group (a) represents a hydrogen atom or a counter cation.
• the multiple M's may be the same or different.
• ⁇ 26> The ink composition according to ⁇ 24> or ⁇ 25>, wherein the content of the colorant is 0.1 to 10.0% by mass based on the total mass of the ink composition.
• ⁇ 27> The ink composition according to any one of ⁇ 24> to ⁇ 26>, further comprising a chelating agent.
• ⁇ 28> The ink composition according to ⁇ 27>, wherein the content of the chelating agent is 0.001 to 1.0% by mass based on the total mass in the ink composition.
• ⁇ 29> The ink composition according to any one of ⁇ 24> to ⁇ 28>, further comprising an antiseptic.
• ⁇ 30> The ink composition according to ⁇ 29>, wherein the content of the preservative is 0.001 to 0.5% by mass based on the total mass of the ink composition.
• ⁇ 31> The ink composition according to any one of ⁇ 24> to ⁇ 30>, further comprising a buffering agent.
• ⁇ 32> The ink composition according to any one of ⁇ 24> to ⁇ 31>, having a pH value of 6.5 to 9.0 at 25°C.
• An ink composition for inkjet recording comprising the ink composition according to any one of ⁇ 24> to ⁇ 32>.
• An inkjet recording method comprising the step of ejecting the ink composition for inkjet recording according to ⁇ 33> using an inkjet recording head.
• an aqueous additive solution for an ink composition, an aqueous colorant solution and an ink composition for an ink composition, an ink composition for inkjet recording containing the ink composition, and an inkjet recording method using the ink composition for inkjet recording be able to.
• An aqueous additive solution for an ink composition of the present invention (also referred to simply as an "additive aqueous solution”) comprises a compound represented by the following general formula (A), a compound represented by the following general formula (II), and water. contains.
• T 1 , T 2 and T 3 are each independently *-NH-(CH 2 ) n -Rt, *-NH-(CH 2 ) n -OH, *-N- ⁇ (CH 2 ) n —OH ⁇ 2 , *—NH—CH 2 CH(OH)CH 2 —Rt, *—OM, a halogen atom, or a substituted or unsubstituted arylamino group.
• T 1 , T 2 and T 3 is *-NH-(CH 2 ) n -Rt, *-NH-(CH 2 ) n -OH, *-N- ⁇ (CH 2 ) n —OH ⁇ 2 or *—NH—CH 2 CH(OH)CH 2 —Rt.
• * represents a binding site to the triazine ring
• n represents an integer from 1 to 5
• Rt represents CO 2 M, SO 3 M, or PO(OM) 2 .
• M represents a hydrogen atom or a counter cation. When there are multiple n's, the multiple n's may be the same or different. When there are multiple M's, the multiple M's may be the same or different.
• Ar 20 represents a benzene ring or a naphthalene ring.
• R 21 to R 28 each independently represent a hydrogen atom or a substituent.
• R 21 and R 22 may combine to form a ring.
• R 23 and R 24 may combine to form a ring.
• R 25 and R 26 may combine to form a ring.
• R 27 and R 28 may combine to form a ring.
• R29 represents a substituent.
• k represents an integer of 0-4.
• Ar 20 represents a naphthalene ring
• k represents an integer of 0-6.
• the multiple R 29 may be the same or different.
• multiple R 29 may combine to form a ring.
• the compound represented by general formula (II) has at least one hydrophilic group.
• the compound represented by the general formula (A) and the compound represented by the general formula (II) can be used as additives in the ink composition.
• the additive aqueous solution of the present invention can be used for preparing an ink composition, and is particularly preferably used for preparing an ink composition for inkjet recording.
• the aqueous additive solution of the present invention and the ink composition prepared using the aqueous additive solution of the present invention are excellent in storage stability.
• T 1 , T 2 and T 3 are each independently *-NH-(CH 2 ) n -Rt, *-NH-(CH 2 ) n -OH, *-N- ⁇ (CH 2 ) n —OH ⁇ 2 , *—NH—CH 2 CH(OH)CH 2 —Rt, *—OM, a halogen atom, or a substituted or unsubstituted arylamino group.
• T 1 , T 2 and T 3 is *-NH-(CH 2 ) n -Rt, *-NH-(CH 2 ) n -OH, *-N- ⁇ (CH 2 ) n —OH ⁇ 2 or *—NH—CH 2 CH(OH)CH 2 —Rt.
• * represents a binding site to the triazine ring
• n represents an integer from 1 to 5
• Rt represents CO 2 M, SO 3 M, or PO(OM) 2 .
• M represents a hydrogen atom or a counter cation. When there are multiple n's, the multiple n's may be the same or different. When there are multiple M's, the multiple M's may be the same or different.
• T 1 , T 2 and T 3 are each independently *-NH-(CH 2 ) n -Rt, *-NH-(CH 2 ) n -OH, *-N- ⁇ (CH 2 ) n —OH ⁇ 2 , *—NH—CH 2 CH(OH)CH 2 —Rt, *—OM, a halogen atom, or a substituted or unsubstituted arylamino group.
• a chlorine atom is preferable as the halogen atom.
• the arylamino group is preferably an arylamino group having 6 to 20 carbon atoms, more preferably an arylamino group having 6 to 10 carbon atoms, and even more preferably a phenylamino group.
• the arylamino group may have a substituent, and the substituent is not particularly limited, but an amino group is preferred. provided that at least one of T 1 , T 2 and T 3 is *-NH-(CH 2 ) n -Rt, *-NH-(CH 2 ) n -OH, *-N- ⁇ (CH 2 ) n —OH) ⁇ 2 or *—NH—CH 2 CH(OH)CH 2 —Rt.
• T 1 , T 2 and T 3 is *-NH-(CH 2 ) n -Rt, *-NH-(CH 2 ) n -OH, *-N- ⁇ (CH 2 ) n -OH) ⁇ 2 , or *—NH—CH 2 CH(OH)CH 2 —Rt
• two of T 1 , T 2 and T 3 are *—NH—(CH 2 ) n —Rt, *-NH-(CH 2 ) n -OH, *-N- ⁇ (CH 2 ) n -OH) ⁇ 2 , or *-NH-CH 2 CH(OH)CH 2 -Rt
• All of T 1 , T 2 and T 3 are *-NH-(CH 2 ) n -Rt, *-NH-(CH 2 ) n -OH, *-N-((CH 2 ) n -OH) 2 , or *—NH—CH 2 CH(OH)CH 2 —Rt.
• n an integer of 1 to 5, and from the viewpoint of inexpensive availability of raw materials for the compound represented by formula (A), water solubility, and storage stability in the ink composition for inkjet recording, 2 to 4 It more preferably represents an integer, even more preferably 2 or 3, and most preferably 2.
• M represents a hydrogen atom or a counter cation.
• M may be single or may be a mixture of multiple types.
• the multiple Ms may be the same or different.
• the compound (A) can also take the form of an inner salt.
• M represents a hydrogen atom or a counter cation.
• the counter cation is not particularly limited, and examples thereof include alkali metal ions, ammonium ions, and organic cations (eg, tetramethylammonium, guanidinium, pyridinium, etc.).
• M is preferably a hydrogen atom, an alkali metal ion or an ammonium ion, more preferably an alkali metal ion or an ammonium ion, still more preferably a lithium ion, a sodium ion or a potassium ion, a lithium ion or a sodium ion is particularly preferred, and lithium ion is most preferred.
• M represents a specific cation (for example, lithium ion)
• M can include hydrogen atoms, alkali metal ions (eg, sodium ions, potassium ions), ammonium ions, 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, with respect to the entire M, and the upper limit is is preferably 100%.
• lithium ion When a specific cation represents something other than lithium ion (for example, sodium ion), it is the same as the case of lithium ion.
• Compound (A) is preferably a compound having an ionic hydrophilic group that enhances water solubility for the purpose of being used as an aqueous solution.
• Ionic hydrophilic groups include sulfo groups (--SO 3 M), carboxy groups (--CO 2 M), phosphate groups (--PO(OM) 2 ) and hydroxyl groups (--OM).
• a sulfo group (--SO 3 M), a carboxy group (--CO 2 M), and a hydroxyl group (--OM) are preferred, and a sulfo group (--SO 3 M) and a hydroxyl group (--OM) are preferred.
• a sulfo group (--SO 3 M).
• M is as described above.
• a lithium salt of a sulfo group (--SO 3 Li) is particularly preferred because it enhances the water solubility of the compound and improves the solution stability.
• the ionic hydrophilic group may be in a free acid state, a salt state, or a mixture of free acid and salt.
• the salt when the compound is a salt, dissolves into ions in a water-soluble state and exists.
• it has an ionic hydrophilic group with a high acid dissociation constant (pKa), most of it may be dissociated and partially dissolved in water in a salt (non-dissociated) state.
• the compound represented by general formula (A) is preferably at least one compound selected from the following compound group (a).
• the charge positions of the cations and anions are illustrated by localized chemical structural formulas, but all possible extreme chemical structures within the scope of the common sense of organic chemistry can be included. can.
• M in the compounds of the compound group (a) represents a hydrogen atom or a counter cation.
• the multiple M's may be the same or different.
• M is as described above.
• Compound (A) is obtained by a known method (e.g., the method described in Japanese Patent No. 4686151) alone or in combination, and if necessary, a reverse osmosis membrane purification method, a gel filtration chromatography purification method, or a preparative method. It can be easily synthesized, isolated and purified by applying a high performance liquid chromatography purification method. Specific examples of representative synthesis schemes of compound (A) are shown below, but are not limited thereto. Using cyanuric chloride as a raw material, a compound having an s-triazine ring can be easily synthesized by a single or a combination of known methods.
• the three types of substituents on the s-triazine ring can be selected by known methods (e.g., pH value of the system during reaction, substituents to be introduced, etc.) can be induced with good selectivity depending on the nucleophilicity of and the order of introduction of substituents.
• R 1 , R 2 , R 3 , R 4 , R 5 and R 6 above each independently represent a hydrogen atom or a corresponding substituent in compound (A).
• M has the same meaning as in compound (A).
• the aforementioned compound (a)-2 corresponds to the compound represented by (c) above, and can be synthesized according to the above synthesis scheme.
• the above compounds (a)-1, (a)-3, (a)-7 to (a)-20, (a)-22, and (a)-23 are the compounds represented by (d) above. and can be synthesized according to the above synthesis scheme.
• the aforementioned compound (a)-4 corresponds to the compound represented by (f) above, and can be synthesized according to the above synthesis scheme.
• the aforementioned compound (a)-21 corresponds to the compound represented by (g) above, and can be synthesized according to the above synthesis scheme.
• the compounds (a)-5 and (a)-6 described above correspond to the compounds represented by (i) above, and can be synthesized according to the above synthesis scheme.
• the content of the compound (A) in the additive aqueous solution of the present invention (the total amount of the compound (A) when two or more types of the compound (A) are contained) is 0.5% based on the total mass of the additive aqueous solution. It is preferably from 01 to 1.0% by mass, more preferably from 0.05 to 1.0% by mass, and particularly preferably from 0.1 to 1.0% by mass.
• the content of the compound (A) in the additive aqueous solution is 0.01% by mass or more, the intermolecular interaction with the compound represented by the general formula (II) in the additive aqueous solution becomes strong ( compatibility is increased), and the effect of long-term aqueous solution stability of the compound represented by general formula (II) is more likely to be exhibited.
• the content of the compound (A) in the additive aqueous solution is 1.0% by mass or less, the solid content concentration in the additive aqueous solution does not increase, and the liquid physical properties during storage of the additive aqueous solution are The fluctuation range over time is reduced, and the continuous ejection stability (reliability) of the ink composition for inkjet recording prepared using the additive aqueous solution is improved.
• Ar 20 represents a benzene ring or a naphthalene ring.
• R 21 to R 28 each independently represent a hydrogen atom or a substituent.
• R 21 and R 22 may combine to form a ring.
• R 23 and R 24 may combine to form a ring.
• R 25 and R 26 may combine to form a ring.
• R 27 and R 28 may combine to form a ring.
• R29 represents a substituent.
• k represents an integer of 0-4.
• Ar 20 represents a naphthalene ring
• k represents an integer of 0-6.
• the multiple R 29 may be the same or different.
• multiple R 29 may combine to form a ring.
• the compound represented by general formula (II) has at least one hydrophilic group.
• the compound represented by general formula (II) is preferably a colorless water-soluble planar compound having more than 10 delocalized ⁇ electrons in one molecule.
• the term "colorless" includes a state in which the image is slightly colored as long as the image is not affected.
• the water-soluble compound represented by the general formula (II) may be a fluorescent compound, but is preferably a non-fluorescent compound, more preferably the absorption peak wavelength ( ⁇ max) on the longest wavelength side is 350 nm.
• a compound having a light absorption coefficient of 320 nm or less and a molar extinction coefficient of 10,000 or less is more preferable.
• 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 is preferably 80 or less, more preferably 50 or less, particularly 30 or less. preferable. Also, more than 10 ⁇ electrons may form one large delocalized system, or may form two or more delocalized systems.
• the compound represented by general formula (II) is preferably water-soluble, and is preferably a compound that dissolves at least 1 g in 100 g of water at 20°C. A compound that dissolves 5 g or more is more preferred, and a compound that dissolves 10 g or more is most preferred.
• the compound represented by general formula (II) has at least one hydrophilic group in one molecule.
• the compound represented by general formula (II) preferably has at least two hydrophilic groups in one molecule.
• Hydrophilic groups include sulfo group (--SO 3 M), carboxy group (--CO 2 M), hydroxy group (--OM), phosphoric acid group (--PO(OM) 2 ), carbonamide group and sulfonamide group. , quaternary ammonium groups, and the like, but are not limited to these.
• hydrophilic group an ionic hydrophilic group is preferred, a sulfo group (--SO 3 M) and a carboxy group (--CO 2 M) are more preferred, and a sulfo group (--SO 3 M) is most preferred.
• M represents a hydrogen atom or a counter cation.
• the counter cation is not particularly limited, and examples thereof include alkali metal ions, ammonium ions, and organic cations (eg, tetramethylammonium, guanidinium, pyridinium, etc.).
• M is preferably a hydrogen atom, an ammonium ion or an alkali metal ion, more preferably an alkali metal ion, still more preferably a lithium ion, a sodium ion or a potassium ion, and a lithium ion or a sodium ion. is particularly preferred.
• the counter cation may be a single salt or a mixed salt.
• the compound represented by formula (II) preferably has 1 to 10, more preferably 2 to 8, hydrophilic groups in one molecule.
• the compound represented by general formula (II) preferably has 2 to 6, more preferably 2 to 4, ionic hydrophilic groups in one molecule.
• At least one of R 21 to R 29 in general formula (II) preferably has an ionic hydrophilic group, more preferably —SO 3 M, and 2 to 6 of R 21 to R 29 are It is more preferred to have —SO 3 M, and it is particularly preferred that 2 to 4 of R 21 to R 29 have —SO 3 M.
• R 21 to R 28 each independently represent a hydrogen atom or a substituent, and the substituents include an alkyl group, an aryl group, an aralkyl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino groups (including anilino groups and heterocyclic amino groups), acyl groups, acylamino groups, ureido groups, halogen atoms, sulfamoyl groups, carbamoyl groups, sulfonamide groups, sulfonyl groups, sulfenyl groups, sulfinyl groups, and the aforementioned hydrophilic groups etc. can be mentioned.
• R 21 to R 28 preferably independently represents 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. From the viewpoint of storage stability, the alkyl group preferably has the hydrophilic group described above as a substituent.
• R 21 and R 22 , R 23 and R 24 , R 25 and R 26 , and R 27 and R 28 may combine to form a ring.
• the ring is not particularly limited, but may be an aromatic ring or a non-aromatic ring, preferably a 5- or 6-membered ring.
• the above ring may contain a heteroatom (eg, an oxygen atom, a nitrogen atom, a sulfur atom) other than the nitrogen atom to which R 21 to R 28 are bonded.
• R 29 represents a substituent, and examples of the substituent include an alkyl group, an aryl group, an aralkyl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group (including an anilino group and a heterocyclic amino group), an acyl group, Examples include acylamino group, ureido group, halogen atom, sulfamoyl group, carbamoyl group, sulfonamide group, sulfonyl group, sulphenyl group, sulfinyl group, and the aforementioned hydrophilic groups.
• substituents can further have one or more substituents
• groups having substituents selected from the above-described substituents as the additional substituents are also included in the examples of the above substituents.
• the multiple R 29 may be the same or different.
• multiple R 29 may combine to form a ring.
• the ring is not particularly limited, but may be an aromatic ring or a non-aromatic ring, preferably a 5- or 6-membered ring.
• the ring may also contain a heteroatom (eg, oxygen atom, nitrogen atom, sulfur atom).
• Ar 20 represents a benzene ring or a naphthalene ring, preferably a benzene ring.
• k represents an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1.
• k represents an integer of 0 to 6, preferably an integer of 0 to 4, more preferably an integer of 0 to 2, more preferably 0 or 1 preferable.
• the content of compound (II) in the additive aqueous solution of the present invention (the total amount of compound (II) when two or more types of compound (II) are contained) is 5.5% based on the total mass of the additive aqueous solution. It is preferably from 0 to 20.0% by mass, more preferably from 10.0 to 20.0% by mass, and most preferably from 12.0 to 18.0% by mass.
• Compound (II) is obtained by a known method (e.g., the method described in Japanese Patent No. 4686151) alone or in combination, and if necessary, a reverse osmosis membrane purification method, a gel filtration chromatography purification method, or a preparative method. It can be easily synthesized, isolated and purified by applying a high performance liquid chromatography purification method.
• the additive aqueous solution 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 inorganic or metal cations (particularly preferably polyvalent cations) to form a chelate compound.
• the chelating agent has the function of preventing the formation and growth of insoluble precipitated foreign matter in the additive aqueous solution and ink composition derived from inorganic or metal cations (especially polyvalent cations) (that is, it functions as a solubilizer). do).
• the additive aqueous solution of the present invention contains a chelating agent, the additive aqueous solution and the ink composition using the additive aqueous solution can be inhibited from being precipitated during long-term storage. And when printing with an inkjet printer using the ink composition for inkjet recording using the ink composition, it is possible to obtain a high-quality printed matter without ink clogging in the nozzle or the like.
• the chelating agent that can be used in the present invention is not particularly limited, and various agents can be used.
• the chelating agent it is possible to use a chelating action to form a complex with cations present in the additive aqueous solution and the ink composition, thereby suppressing the generation and growth of precipitated foreign matter in the additive aqueous solution and the ink composition.
• solubilizers can be used singly or in combination, but water-soluble compounds are preferred.
• Chelating agents include, for example, ethylenediaminetetraacetic acid (EDTA) or salts thereof (e.g., EDTA-4 sodium (tetrasodium salt), EDTA-4lithium (tetralithium salt), etc.), picolinic acid or salts thereof (e.g., picoline quinolinic acid or its salts (e.g., sodium quinolinate), 1,10-phenanthroline, 8-hydroxyquinoline, tetrasodium 3-hydroxy-2,2′-iminodisuccinate, methylglycine diacetic acid (MGDA) or salts thereof, L-glutamic acid diacetic acid (GLDA) or salts thereof, L-aspartic acid diacetic acid (ASDA) or salts thereof, hydroxyethylimino diacetic acid (HIDA) or salts thereof, 3-hydroxy-2,2'-iminodisuccinate acid (HIDS) or salts thereof, dicarboxymethylglutamic acid (CMGA)
• Salts of the above chelating agents are preferably monovalent metal salts such as sodium, potassium and lithium, as well as salts such as ammonium and amine.
• these chelating agents show even less attenuation of the chelating action against pH changes of the additive aqueous solution and the ink composition. Therefore, the chelating action is exhibited in a wider range of pH, and for example, it is possible to further improve the adaptability of the additive aqueous solution and the ink composition to pH changes such as changes over time.
• the content of the chelating agent is preferably 0.001 to 1.0% by mass, more preferably 0.01 to 0.5% by mass, based on the total mass of the additive aqueous solution. 01 to 0.1 mass % is particularly preferred.
• the content of the chelating agent is 0.001% by mass or more, the chelating action can be effectively expressed. It is possible to suppress the excessive increase of the pH and the excessive increase of the pH.
• the additive aqueous solution of the present invention can be prepared using water as a medium. If necessary, it can also be prepared by using a lipophilic medium or an aqueous medium and dissolving or dispersing compound (A) and compound (II) therein.
• Examples of the water contained in the additive aqueous solution of the present invention include pure water such as ion-exchanged water, ultrafiltrated water, reverse osmosis water, distilled water, and ultrapure water.
• the content of water in the additive aqueous solution of the present invention is not particularly limited, but from the viewpoint of storage stability, it is preferably 50 to 95% by mass, preferably 60 to 95% by mass, based on the total mass of the additive aqueous solution. %, more preferably 70 to 95% by mass, and particularly preferably 80 to 95% by mass.
• the aqueous additive solution of the present invention can contain other solvents in addition to water.
• water-miscible organic solvents are preferred.
• water-miscible organic solvents include alcohols (e.g., methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol), polyhydric alcohols (e.g.
• glycol ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol), glycol derivatives (e.g.
• ethanolamine diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyl diethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine, triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine) and other polar solvents (e.g.
• the content of the water-miscible organic solvent is preferably 0.01 to 50% by mass based on the total mass of the additive aqueous solution. , more preferably 0.01 to 30% by mass, and even more preferably 0.01 to 20% by mass.
• preservative refers to an agent that has the function of preventing the occurrence and growth of microorganisms, particularly bacteria and fungi (molds). Preservatives also include antifungal agents.
• the additive aqueous solution of the present invention may contain a preservative. By using a preservative in the additive aqueous solution of the present invention, it is possible to suppress the generation and growth of bacteria and mold even during long-term storage of the additive aqueous solution, and ink for inkjet recording using the additive aqueous solution after long-term storage. When the composition is used for printing with an inkjet printer, clogging of nozzles and the like with ink is unlikely to occur, making it possible to obtain high-quality prints.
• Various preservatives can be used in the present invention.
• antiseptics include inorganic antiseptics containing heavy metal ions (such as those containing silver ions) and salts.
• Organic preservatives include quaternary ammonium salts (tetrabutylammonium chloride, cetylpyridinium chloride, benzyltrimethylammonium chloride, etc.), phenol derivatives (phenol, cresol, butylphenol, xylenol, bisphenol, etc.), phenoxy ether derivatives (phenoxyethanol etc.), heterocyclic compounds (benzotriazole, PROXEL, 1,2-benzisothiazolin-3-one, etc.), alkanediols (pentylene glycol (1,2-pentanediol), isopentyldiol (3- methyl-1,3-butanediol), hexanediol (1,2-hexanediol), etc.), caprylyl glycol (1,2-octanedio
• the preservative it is preferable to use at least one preservative selected from the group consisting of heterocyclic compounds, phenol derivatives, phenoxy ether derivatives and alkanediols.
• preservatives those described in Antibacterial and Antifungal Handbook (Gihodo: 1986), Antibacterial and Antifungal Encyclopedia (edited by the Encyclopedia of the Antibacterial and Antifungal Society of Japan), etc. can also be used.
• the aqueous additive solution of the present invention may contain two or more preservatives.
• the storage stability, particularly hue stability, of recorded images formed using an aqueous additive solution and an ink composition for inkjet recording using an aqueous additive solution is improved.
• the effects of the present invention are exhibited even better, such as markedly improved ink ejection stability when printing with an inkjet printer using an inkjet recording ink composition using an aqueous additive solution after long-term storage.
• the contact of bacteria and mold with two or more kinds of preservatives suppresses the acquisition of resistance of the bacteria and mold to individual preservatives.
• the preservatives have skeletons with different chemical structures.
• at least one kind of preservative is preferably a heterocyclic compound, a phenol derivative, a phenoxyether derivative, or an alkanediol, especially a heterocyclic compound. Preferably.
• a combination of a heterocyclic compound and a phenoxy ether derivative, a combination of a heterocyclic compound and a phenol derivative, a combination of a heterocyclic compound and an alkanediol, and the like are preferable.
• the heterocyclic compound is preferably a thiazole-based compound or a benzotriazole-based compound.
• a thiazole-based compound functions particularly as an antifungal agent among antiseptic agents.
• Thiazole compounds include benzisothiazoline, isothiazoline, 1,2-benzisothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-(thiocyanomethylthio)benzthiazole, 2- Mercaptobenzthiazole and 3-allyloxy-1,2-benzisothiazole-1,1-oxide and the like can be mentioned.
• PROXEL registered trademark
• BDN BD20, GXL, LV, XL2, XL2(s), Ultra10, etc.
• LONZA Co., Ltd. can also be used as a thiazole antifungal agent.
• the benzotriazole-based compound also functions as an anticorrosive agent, and for example, the metal material (particularly, 42 alloy (nickel-iron alloy containing 42% nickel)) constituting the inkjet head is combined with the additive aqueous solution and the ink composition. It is possible to prevent the occurrence of rust, which is one of the causes of contact.
• Benzotriazole compounds include 1H-benzotriazole, 4-methyl-1H-benzotriazole, 5-methyl-1H-benzotriazole and sodium salts or potassium salts thereof.
• the content ratio when two or more preservatives are combined is not particularly limited, but the content of each preservative is preferably 1% by mass or more of the total content of preservatives. It is more preferably at least 20% by mass, even more preferably at least 20% by mass.
• the content of each preservative is preferably 99% by mass or less, more preferably 90% by mass or less, and even more preferably 80% by mass or less of the total content of the preservatives.
• the effect of each preservative can be efficiently obtained, and a synergistic effect between the preservatives can be easily obtained.
• the content of the preservative (the total content when two or more preservatives are contained) is not particularly limited, but based on the total amount of the additive aqueous solution, It is preferably 0.001 to 1.0% by mass, more preferably 0.005 to 1.0% by mass, even more preferably 0.01 to 1.0% by mass, and 0.01 ⁇ 0.5% by weight is particularly preferred, and 0.01 to 0.4% by weight is most preferred.
• the amount within the above range, the effect of the antiseptic can be obtained more efficiently, and water putrefaction and precipitation can be suppressed.
• the mass ratio of the preservative to the total amount of compound (A) and compound (II) (compound (A) + compound (II))/preservative is 90/10 to 99/1.
• compound (A) and compound (II) are stably dissolved in the additive aqueous solution of the present invention, and the effect of preventing the generation and growth of bacteria and fungi (mold) can be achieved at the same time. .
• the additive aqueous solution of the present invention may contain a buffering agent (pH value stabilizer).
• pH value stabilizer a buffering agent
• the additive aqueous solution of the present invention is weakly acidic to neutral to basic.
• it is neutral to basic, more preferably neutral to weakly basic, and most preferably weakly basic.
• the pH value of the additive aqueous solution at 25° C. is preferably 6.5 to 9.0, more preferably 6.8 to 9.0, and 7.0 to 9.0. is most preferred.
• the pH value of the additive aqueous solution at 25°C is 6.5 or more, the dissolution stability is improved when the additive aqueous solution and the ink composition are prepared, and the generation of precipitates is suppressed.
• the pH value of the additive aqueous solution at 25° C. is 9.0 or less, the aqueous coloring agent solution for the ink composition containing the coloring agent in the additive aqueous solution, and one of the coloring agents used in the ink composition. The possibility of decomposition of the part is reduced, and the storage stability and reliability of the colorant aqueous solution for the ink composition and the ink composition are improved.
• the buffering agent (pH value stabilizer) is not particularly limited as long as it is a buffering agent that suppresses fluctuations in the pH value in the additive aqueous solution.
• preferred buffering agents include lithium carbonate, lithium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, acetic acid/triethylamine mixtures, phosphoric acid/triethylamine mixtures, and the like.
• the buffering agent is preferably lithium carbonate, lithium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate, potassium carbonate or potassium hydrogen carbonate, more preferably sodium carbonate, sodium hydrogen carbonate, potassium carbonate or potassium hydrogen carbonate, most preferably sodium hydrogen carbonate. preferable.
• the additive aqueous solution 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 accelerators, UV absorbers, surface tension modifiers, antifoaming agents, viscosity modifiers, dispersants, dispersing agents, Known additives such as stabilizers, rust inhibitors and pH adjusters (described in JP-A-2003-306623) can be mentioned.
• the additive aqueous solution of the present invention is usually a colorless aqueous solution when it does not contain a coloring agent.
• the aqueous additive solution of the present invention can be used to prepare various colorless and colored ink compositions. For example, yellow-tone ink composition, orange-tone ink composition, magenta-tone ink composition, cyan-tone ink composition, gray-tone ink composition, black-tone ink composition, brown-tone ink composition, red-tone ink composition, green It can be used for a color ink composition, a blue color ink composition, a metalink color ink composition, and the like.
• the aqueous additive solution of the present invention can be used not only as a colorless aqueous additive solution, but also can be added to an aqueous colorant solution for the purpose of improving the storage stability of the colorant.
• the aqueous colorant solution for the ink composition of the present invention (also referred to simply as "aqueous colorant solution”) is obtained by adding the additive aqueous solution of the present invention to the aqueous solution of the colorant. That is, the aqueous colorant solution of the present invention contains the compound represented by the general formula (A), the compound represented by the general formula (II), water, and a colorant.
• the aqueous colorant solution of the present invention may further contain water-miscible organic solvents, chelating agents, preservatives, and buffering agents.
• the water-miscible organic solvent, chelating agent, preservative, and buffer are the same as those described in the additive aqueous solution.
• the aqueous colorant solution of the present invention may further contain other additives.
• Other additives that may be contained in the aqueous colorant solution of the present invention are the same as those described in the description of the aqueous additive solution.
• the preferred ranges of the content of water, water-miscible organic solvent, chelating agent, and preservative in the aqueous colorant solution are the same as the preferred ranges of the content of each component in the aqueous additive solution (additional mixing ratio).
• the pH value of the colorant aqueous solution at 25° C. is preferably 6.5 to 9.0, more preferably 6.8 to 9.0, and more preferably 7.0 to 9.0. Most preferred.
• the content of compound (A) in the aqueous colorant solution of the present invention (the total amount of compound (A) when two or more types of compound (A) are contained) is 0.00% based on the total mass of the aqueous colorant solution. 001 to 0.3 mass %, more preferably 0.005 to 0.1 mass %, and particularly preferably 0.01 to 0.05 mass %.
• the content of the compound (A) in the aqueous coloring agent solution is 0.3% by mass or less, the solid content concentration in the aqueous coloring agent solution does not increase, and the liquid physical properties when the aqueous coloring agent solution is stored are It is thought that the fluctuation width of the colorant over time becomes smaller, and the continuous ejection stability (reliability) of the ink composition for inkjet recording prepared using the colorant aqueous solution is improved.
• the content of compound (II) in the aqueous colorant solution of the present invention (the total amount of compound (II) when two or more types of compound (II) are contained) is 0.5% based on the total mass of the aqueous colorant solution. It is preferably 5 to 8.0% by mass, more preferably 0.9 to 7.5% by mass, and most preferably 0.95 to 3.0% by mass.
• the content of the compound (II) in the aqueous coloring agent solution is 8.0% by mass or less, the solid content concentration in the aqueous coloring agent solution does not increase, and the liquid physical properties when the aqueous coloring agent solution is stored are is considered to be extremely small, and the continuous ejection stability (reliability) of the ink composition for inkjet recording prepared using the aqueous colorant solution is improved.
• the coloring agent used in the coloring agent aqueous solution dyes are preferable, and water-soluble dyes are more preferable.
• the content of the colorant in the aqueous colorant solution of the present invention is preferably 5.0 to 20.0% by mass based on the total mass of the aqueous colorant solution.
• the content of the coloring agent in the aqueous coloring agent solution is 20.0% by mass or less, the concentration of solids in the aqueous coloring agent solution does not increase, and the liquid physical properties of the aqueous coloring agent solution do not increase over time. It is believed that the width of fluctuation is reduced, and the continuous ejection stability (reliability) of the ink composition for inkjet recording prepared using the aqueous colorant solution is improved.
• the aqueous colorant solution of the present invention can be an aqueous colorant solution with various tones. It is particularly suitable for aqueous solutions, or aqueous colorant solutions for black-tone ink compositions.
• aqueous colorant solution of the present invention is an aqueous colorant solution for a cyan-tone ink composition, an aqueous colorant solution for a gray-tone ink composition, and an aqueous colorant solution for a black-tone ink composition, preferred colorants will be described respectively.
• the coloring agent is preferably a dye, more preferably a water-soluble dye. It is most preferred from the viewpoint of long-term storage stability of the aqueous solution.
• Hydrophilic groups include sulfo group (--SO 3 M), carboxy group (--CO 2 M), hydroxy group (--OM), phosphoric acid group (--PO(OM) 2 ), carbonamide group and sulfonamide group. , quaternary ammonium groups, and the like, but are not limited to these.
• hydrophilic group an ionic hydrophilic group is preferred, a sulfo group (--SO 3 M) and a carboxy group (--CO 2 M) are more preferred, and a sulfo group (--SO 3 M) is most preferred.
• M represents a hydrogen atom or a counter cation.
• the counter cation is not particularly limited, and examples thereof include alkali metal ions, ammonium ions, and organic cations (eg, tetramethylammonium, guanidinium, pyridinium, etc.).
• M is preferably a hydrogen atom, an ammonium ion or an alkali metal ion, more preferably an alkali metal ion, still more preferably a lithium ion, a sodium ion or a potassium ion, and a lithium ion or a sodium ion. is particularly preferred.
• the counter cation may be a single salt or a mixed salt.
• the colorant preferably has 1 to 10, more preferably 2 to 5, hydrophilic groups in one molecule of the water-soluble dye.
• aqueous colorant solution of the present invention is an aqueous colorant solution for a cyan tone ink composition
• examples of the colorant include those described in Japanese Patent No. 3949385, Japanese Patent No. 4145153, and International Publication No. 2021/039651. Cyan dyes are preferred.
• the content of the colorant is 5.0 to 20.0% by mass based on the total mass of the aqueous colorant solution. is preferably 5.0 to 15.0% by mass, more preferably 5.0 to 12.0% by mass, particularly 5.0 to 10.0% by mass preferable.
• the content of the colorant in the aqueous colorant solution for the cyan ink composition is 5.0% by mass or more, not only is it easy to prepare the light/dark cyan colorant ink composition, but also the aqueous colorant solution can be obtained. It is considered that the effect of long-term dissolution stability is more likely to be exhibited.
• the content of the colorant in the aqueous colorant solution for the cyan ink composition is 20.0% by mass or less, the concentration of solids in the aqueous colorant solution does not increase, and when the aqueous colorant solution is stored,
• the fluctuation range of the liquid properties over time in particular, dissolution stability, absorbance change, viscosity increase/decrease, pH value change
• the continuous ejection stability will improve.
• the content of the colorant is preferably 5.0 to 20.0% by mass based on the total mass of the aqueous colorant solution. , more preferably 5.0 to 15.0% by mass, still more preferably 8.0 to 12.0% by mass, and particularly preferably 8.0 to 10.0% by mass.
• the content of the colorant is preferably 5.0 to 20.0% by mass based on the total mass of the aqueous colorant solution. , more preferably 8.0 to 15.0% by mass, even more preferably 10.0 to 15.0% by mass, and particularly preferably 10.0 to 12.0% by mass.
• the aqueous colorant solution of the present invention is an aqueous colorant solution for a gray-tone ink composition or an aqueous colorant solution for a black-tone ink composition (these are also collectively referred to as "aqueous colorant solution for a gray-black tone ink composition").
• the coloring agent is preferably, for example, a coloring agent (gray dye or black dye) represented by general formula (I) described in JP-A-2020-76048.
• the content of the colorant is 5.0 to 20.0% by mass based on the total mass of the aqueous colorant solution. It is preferably 5.0 to 15.0% by mass, more preferably 5.0 to 12.0% by mass, and 5.0 to 10.0% by mass. is particularly preferred.
• the content of the coloring agent in the aqueous coloring agent solution for the gray/black ink composition is 5.0% by mass or more, not only is the preparation of the gray/black ink composition easy, but also coloring is achieved. It is considered that the effect of long-term dissolution stability of the agent aqueous solution is more likely to be exhibited.
• the content of the colorant in the aqueous colorant solution for the gray/black tone ink composition is 20.0% by mass or less, the solid content concentration in the aqueous colorant solution does not increase, and the aqueous colorant solution can be preserved.
• the content of the colorant is preferably 5.0 to 20.0% by mass based on the total mass of the aqueous colorant solution. It is more preferably 5.0 to 15.0% by mass, even more preferably 7.0 to 12.0% by mass, and particularly preferably 7.5 to 10.0% by mass.
• the content of the colorant is preferably 5.0 to 20.0% by mass based on the total mass of the aqueous colorant solution. It is more preferably 5.0 to 15.0% by mass, even more preferably 5.3 to 15.0% by mass, and particularly preferably 10.0 to 12.0% by mass.
• the coloring agent aqueous solution of the present invention may further contain a toning agent in addition to the coloring agents described above.
• a toning agent in addition to the coloring agents described above.
• the aqueous colorant solution is an aqueous colorant solution for a gray/black tone ink composition, it preferably contains a toning agent.
• Examples of the toning agent that can be used when the aqueous coloring agent solution of the present invention is an aqueous coloring agent solution for a gray/black tone ink composition include: and toning agents. Specific examples of preferred toning agents are listed below, but are not limited to these.
• the content of the toning agent is 0.1 to 2.0% by mass based on the total mass of the aqueous colorant solution. is preferably 0.3 to 2.0% by mass, more preferably 0.5 to 1.5% by mass, particularly 0.5 to 1.3% by mass Preferably, 0.8 to 1.2% by weight is most preferred.
• the above range is preferable from the viewpoint of hue adjustment (neutral gray toning) with the colorant coexisting in the aqueous solution of the colorant.
• the content of the toning agent is 0.1 to 5.0% by mass based on the total mass of the aqueous colorant solution. is preferably 0.3 to 3.5% by mass, more preferably 0.5 to 3.0% by mass, particularly 1.0 to 3.0% by mass Preferably, 1.5 to 2.5% by weight is most preferred.
• the above range is preferable from the viewpoint of hue adjustment (black toning) with the colorant coexisting in the colorant aqueous solution and print density.
• the aqueous colorant solution of the present invention may contain another toning agent instead of or in addition to the above-described toning agent.
• the aqueous colorant solution of the present invention when it is an aqueous colorant solution for a gray-black tone ink composition, it contains a magenta dye as a second toning agent in order to improve the tone from gray to black. is preferred.
• magenta dye examples include the magenta dyes described in JP-A-2020-76048. Specific examples of the second toning agent are listed below, but are not limited to these.
• Me represents a methyl group
• Et represents an ethyl group
• Pr and Pr(i) represent an isopropyl group
• t-Bu represents a tert-butyl group
• C 5 H 11 and C 5 H 11 (n) represent an n-pentyl group
• M represents a hydrogen atom or a counter cation. M is the same as M in the compounds of compound group (a) described above.
• the aqueous coloring agent solution of the present invention contains a magenta dye as the second toning agent
• the content of the magenta dye varies depending on the color value (coloring power per unit mass) of the dye used. It is preferably 0.1 to 5.0% by mass, more preferably 0.5 to 3.0% by mass, based on the total mass.
• the content of the magenta dye is preferably 0.1 to 5.0% by mass based on the total mass of the aqueous colorant solution. preferably 0.3 to 3.5% by mass, more preferably 0.5 to 3.0% by mass, particularly preferably 0.5 to 2.0% by mass, 0.8 to 1.2% by weight is most preferred.
• the above range is preferable from the viewpoint of hue adjustment (neutral gray toning) with the colorant coexisting in the aqueous solution of the colorant.
• the content of the magenta dye is 0.1 to 5.0% by mass based on the total mass of the aqueous colorant solution. Is preferably 0.3 to 3.5% by mass, more preferably 0.5 to 3.0% by mass, particularly preferably 1.0 to 3.0% by mass , 1.5 to 2.5% by weight.
• the above range is preferable from the viewpoint of hue adjustment (black toning) with the colorant coexisting in the colorant aqueous solution and print density.
• the aqueous colorant solution of the present invention may contain another toning agent (third toning agent) in place of or in addition to the above-described toning agent.
• third toning agent is listed below, but are not limited to these.
• toning dyes that can be contained in the aqueous coloring agent solution of the present invention are exemplified below, but are not limited thereto.
• C.I. is an abbreviation for "color index.”
• ⁇ C. I. Direct Yellow 9, 11, 28, 29, 35, 39, 41, 53, 59, 68, 87, 93, 95, 96, 106, 108, 109, 122, 130, 142, 144, 161, 163, etc.
• C.I is an abbreviation for "color index.”
• Acid Yellow 19 39, 49, 50, 61, 64, 79, 110, 127, 135, 143, 151, 159, 169, 174, 190, 195, 196, 197, 199, 218, 219, 222, 227, etc. ⁇ C.
• Reactive Yellow 2 3, 13, 14, 15, 17, 18, 23, 24, 25, 26, 27, 29, 35, 37, 41, 42, etc.
• Basic Yellow 1 2, 4, 11, 13, 14, 15, 19, 21, 23, 24, 25, 28, 29, 32, 36, 39, 40, etc.
• the content of the other toning agents in the aqueous coloring agent solution is determined by the color value of the dye used (per unit mass) although it varies depending on the coloring strength), it is preferably 0.1 to 3.0% by mass, more preferably 0.3 to 1.2% by mass, based on the total mass of the aqueous colorant solution.
• the content of other toning agents is 0.1 to 3.0% by mass based on the total mass of the aqueous colorant solution. is preferably 0.1 to 2.0% by mass, more preferably 0.1 to 1.0% by mass, and 0.3 to 1.0% by mass is particularly preferred, and 0.3 to 0.5% by mass is most preferred.
• the above range is preferable from the viewpoint of hue adjustment (neutral gray toning) with the colorant coexisting in the aqueous solution of the colorant.
• the content of the other toning agent is 0.1 to 3.0% by mass based on the total mass of the aqueous colorant solution. is preferably 0.1 to 2.0% by mass, more preferably 0.1 to 1.5% by mass, and 0.3 to 1.5% by mass is particularly preferred, and 0.3 to 1.2% by mass is most preferred.
• the above range is preferable from the viewpoint of hue adjustment (black toning) with the colorant coexisting in the colorant aqueous solution and print density.
• the additive aqueous solution and the colorant aqueous solution of the present invention described above are used to prepare an ink composition.
• the ink composition include ink compositions as image recording materials for forming images. Specific examples include inkjet recording materials, heat-sensitive recording materials, pressure-sensitive recording materials, electrophotographic recording materials, transfer-type silver halide photosensitive materials, printing inks, recording pens, etc., preferably inkjet recording materials. materials, heat-sensitive recording materials, and electrophotographic recording materials, more preferably inkjet recording materials.
• the ink composition of the present invention is an ink composition containing compound (A), the compound represented by general formula (II), water, and a colorant.
• the ink composition of the present invention can be prepared, for example, using the aforementioned aqueous colorant solution of the present invention. More specifically, for example, by adding a water-miscible organic solvent, other additives (e.g., pH adjuster, surface tension adjuster, etc.), water, etc. to the aqueous solution of the coloring agent of the present invention, the ink composition can be obtained. can be prepared.
• the ink composition of the invention preferably further contains a chelating agent.
• the ink composition of the invention preferably further contains a preservative.
• the ink composition of the invention preferably further contains a buffering agent.
• the compound (A), compound (II), water, colorant, water-miscible organic solvent, chelating agent, preservative, and buffer are the same as those described in the additive aqueous solution and the colorant aqueous solution.
• other components that the ink composition of the present invention may contain are the same as those described in the description of the additive aqueous solution and the colorant aqueous solution.
• the pH value of the ink composition of the present invention at 25° C. is preferably 6.5 to 9.0, more preferably 6.8 to 9.0, and more preferably 7.0 to 9.0. Most preferably there is.
• the content of the preservative in the ink composition of the present invention is preferably 0.001 to 1.0% by mass, more preferably 0.001 to 0.5% by mass, based on the total mass of the ink composition. More preferably, it is more preferably 0.005 to 0.5% by mass, particularly preferably 0.01 to 0.5% by mass, and 0.01 to 0.4% by mass is most preferred.
• the content of the chelating agent in the ink composition of the present invention is preferably 0.001 to 1.0% by mass, more preferably 0.01 to 0.5% by mass, based on the total mass of the ink composition. is more preferable, and 0.01 to 0.1% by mass is particularly preferable.
• the chelating agent and the coloring material means a coloring agent, a toning agent, a magenta dye as a second toning agent, a third toning agent, and other coloring agents that may be used in combination.
• the coloring material means a coloring agent, a toning agent, a magenta dye as a second toning agent, a third toning agent, and other coloring agents that may be used in combination.
• mass-based content of chelating agent mass-based content of coloring material
• Metal salts may be formed by metals that may be mixed in the manufacturing process of the colorant (dye) or contained in the ink container of the ink composition and eluted into the ink composition.
• the above ratio it is possible to effectively suppress the generation of foreign substances that cause clogging of the inkjet head.
• the chelating action can be effectively exhibited, and excessive increase in viscosity of the ink composition and excessive increase in pH can be suppressed.
• the ink composition of the present invention is used for recording and reproducing color images used in displays such as solid-state imaging devices such as CCDs (Charge-Coupled Devices), LCDs (Liquid Crystal Displays), and PDPs (Plasma Display Panels). It can also be applied to dyeing solutions for dyeing filters and various fibers.
• the ink composition of the present invention can be used in recording methods such as printing, copying, marking, writing, drafting and stamping, and is particularly suitable for use in inkjet recording methods.
• the ink composition of the invention is particularly preferably used as an ink composition for inkjet recording.
• the content of the coloring agent in the ink composition of the present invention is preferably 0.1 to 10.0% by mass based on the total mass of the ink composition.
• the ink composition of the present invention contains a cyan dye as a colorant
• the ink composition of the present invention can be used as a cyan tone ink composition for inkjet recording (also referred to simply as "cyan ink"), and can be used as a dark cyan ink. and light cyan ink.
• the dark cyan ink is particularly suitable for photo and document applications.
• the light cyan ink is particularly suitable for forming light cyan images and light mixed (blue, green, gray, etc.) images.
• the content of the coloring agent (cyan dye) in the cyan ink is preferably 2.5 to 10.0% by mass, based on the total mass of the cyan ink, and preferably 3.0 to 10.0% by mass. It is more preferably 8.0% by mass, even more preferably 3.5 to 6.0% by mass, and particularly preferably 3.5 to 5.5% by mass.
• the content of the coloring agent (cyan dye) in the cyan ink is preferably 0.1 to 5.0% by mass, based on the total mass of the cyan ink, and preferably 0.5 to 5.0% by mass. It is more preferably 3.0% by mass, even more preferably 1.0 to 2.5% by mass, and particularly preferably 1.0 to 2.0% by mass.
• the ink composition of the present invention contains a gray dye or a black dye as a colorant
• the ink composition of the present invention can be used as a gray-tone ink composition for inkjet recording (also referred to simply as "gray ink”) or for inkjet recording. It can be used as a black tone ink composition (simply referred to as “black ink”). Black ink is particularly suitable for photo and document applications. Gray inks are particularly suitable for light gray imaging applications.
• the content of the colorant is preferably 0.1 to 10.0% by mass, based on the total mass of the ink composition. It is more preferably 2 to 7.0% by mass, even more preferably 0.3 to 5.0% by mass, particularly preferably 0.3 to 3.0% by mass, and 0.5 to 2.0% by weight is most preferred.
• the intermolecular interaction between the compound (A) and the compound (II) can be enhanced, and the gray hue can be adjusted with the gray toning agent. (Neutral gray toning) is also good.
• the content of the colorant is preferably 0.1 to 10.0% by mass, based on the total mass of the ink composition. It is more preferably 5 to 7.0% by mass, even more preferably 1.0 to 6.0% by mass, particularly preferably 3.0 to 6.0% by mass, and 3.5 to 5.5% by weight is most preferred.
• the content of the colorant in the black ink within the above range, the intermolecular interaction with the compound (A) and the compound (II) can be enhanced, and the black hue can be adjusted with the toning agent for black tone. is also good.
• the content of the toning agent is preferably 0.1 to 10.0% by mass based on the total mass of the ink composition. , more preferably 0.5 to 6.0% by mass.
• the mixing ratio of the content of the colorant, the total content of the compound (A) and the compound (II), and the content of the toning agent, based on the total mass of the ink composition is a colorant / ⁇ compound (A) + compound (II) ⁇ / toning agent of 0.01 to 10.0% by mass / 0.01 to 10.0% by mass / 0.00 to 10.0% by mass %, more preferably 0.05 to 5.0% by mass/0.05 to 5.0% by mass/0.01 to 5.0% by mass.
• the ink composition of the present invention is a dark cyan ink
• the content of the coloring agent, the total content of the compound (A) and the compound (II), and the toning agent based on the total weight of the ink composition
• the compounding ratio of the content is 2.5 to 10.0% by mass/0.25 to 3.0% by mass of colorant/ ⁇ compound (A)+compound (II) ⁇ /toning agent/0.
• the content of the coloring agent, the total content of the compound (A) and the compound (II), and the toning agent, based on the total mass of the ink composition The compounding ratio of the content is 0.1 to 5.0% by mass/0.01 to 2.5% by mass/0.01 to 2.5% by mass of coloring agent/ ⁇ compound (A)+compound (II) ⁇ /toning agent 00 to 1.0% by mass, more preferably 0.5 to 3.0% by mass/0.05 to 1.5% by mass/0.00 to 0.5% by mass, and 1 0 to 2.5% by mass/0.10 to 1.25% by mass/0.00 to 0.10% by mass, more preferably 1.0 to 2.0% by mass/0.10 to 1.0% by mass 0%/0.00-0.05% by weight is most preferred.
• the content of the coloring agent, the total content of the compound (A) and the compound (II), and the content of the toning agent based on the total mass of the ink composition
• the content ratio is 0.10 to 5.0% by mass/0.30 to 5.0% by mass/0.01 for colorant/ ⁇ compound (A)+compound (II) ⁇ /toning agent. ⁇ 2.5% by mass, more preferably 0.30 to 3.0% by mass/0.30 to 3.0% by mass/0.03 to 1.5% by mass, and 0.5% by mass. More preferably, it is 50 to 2.0% by mass/0.50 to 1.5% by mass/0.05 to 1.0% by mass.
• the content of the coloring agent, the total content of the compound (A) and the compound (II), and the content of the toning agent based on the total mass of the ink composition
• the content ratio is 1.0 to 6.0% by mass/0.1 to 3.0% by mass/1.0 ⁇ It is preferably 4.0% by mass, more preferably 3.0 to 5.5% by mass/0.3 to 3.0% by mass/1.0 to 3.0% by mass, and 3.5% by mass. More preferably, it is ⁇ 5.0% by mass/0.3-2.0% by mass/1.5-2.0% by mass.
• the content of the magenta dye is preferably 0.01 to 2.0% by mass, based on the total mass of the ink composition, and preferably 0.03 to 1% by mass. 0% by mass, more preferably 0.05 to 2.0% by mass, particularly preferably 0.05 to 1.0% by mass, and 0.05 to 0.50% by mass. % by weight is most preferred.
• the hue adjustment (neutral gray toning) with the colorant coexisting in the ink composition is improved.
• the content of the magenta dye is preferably 0.10 to 5.0% by weight, preferably 0.50 to 3.0% by weight, based on the total weight of the ink composition.
• % by mass is most preferable from the viewpoint of hue adjustment (black toning) with a colorant coexisting in the ink composition.
• the content of the water-miscible organic solvent is preferably 20 to 50% by mass, based on the total mass of the ink composition. It is more preferably from 30 to 50% by mass, and particularly in the case of an ink composition for inkjet recording, it is particularly preferably from 30 to 40% by mass because of suitability for piezo heads and thermal heads.
• the ink composition for inkjet recording of the present invention includes the ink composition of the present invention described above.
• the ink composition of the present invention described above can also be used as it is as an ink composition for inkjet recording.
• an ink composition for inkjet recording is prepared together with a colorant, whereby a color from gray to black, Alternatively, an image excellent in cyan tone can be formed. It is considered that the colorant forms a relatively stable associated state in the image immediately after being formed.
• the highly water-soluble coloring agent (dye) progresses to a more stable association state with moisture as a driving force (change in the state of existence like the H association of the dye).
• compound (II) which is a compound having high planarity
• a relatively stable state of association of gray to black or cyan colorants in an image immediately after being formed by an inkjet method is achieved.
• the change in the color tone of the image could be suppressed without causing a change in the aggregation state of the colorant due to changes in the surrounding environment (humidity, light, active gas).
• the interaction and compatibility between the colorant and the compound (II) and the compound (A) are improved, thereby dramatically improving the storage stability of the ink composition and improving the antiseptic property. It is thought that it has become possible to minimize fluctuations in pH value, absorbance, viscosity, and surface tension even after long-term storage of the ink composition.
• the inkjet recording method of the present invention has a step of ejecting the ink composition for inkjet recording of the present invention using an inkjet recording head.
• energy is supplied to the ink composition for ink jet recording of the present invention, and known image-receiving materials such as plain paper and resin-coated paper such as JP-A-8-169172 and JP-A-8-27693 are used.
• a polymer fine particle dispersion (also called polymer latex) may be used in combination for the purpose of imparting glossiness and water resistance and improving weather resistance.
• the timing of applying the polymer latex to the image-receiving material may be before, after, or at the same time as the application of the colorant. It may be in an ink, or it may be used as a liquid material of polymer latex alone.
• the method described in the specification can be preferably used.
• the recording method of the ink jet recording method of the present invention is not limited, and known methods such as a charge control method in which ink is ejected using electrostatic attraction, a drop-on-demand method using vibration pressure of a piezoelectric element (pressure pulse method), an acoustic inkjet method in which an electric signal is converted into an acoustic beam to irradiate the ink and ejects the ink using radiation pressure, and a thermal inkjet method in which the ink is heated to form bubbles and the pressure generated is used Used for methods, etc.
• a charge control method in which ink is ejected using electrostatic attraction
• a drop-on-demand method using vibration pressure of a piezoelectric element pressure pulse method
• an acoustic inkjet method in which an electric signal is converted into an acoustic beam to irradiate the ink and ejects the ink using radiation pressure
• thermal inkjet method in which the ink is heated to form bubbles and the
• Inkjet recording methods include a method of ejecting a large number of low-density inks called photo ink in a small volume, a method of improving image quality by using multiple inks of substantially the same hue but different densities, and a method of using colorless and transparent ink. method is included.
• Example 1 (Preparation of additive aqueous solution 1) 0.36 g of compound (a)-1, 0.072 g of compound (a)-2, 0.146 g of compound (a)-3, 14.423 g of compound (P-3), 0.423 g of compound (P-3), chelating agent (EDTA). 065 g, preservative (PROXEL (registered trademark) XL2(s) manufactured by LONZA Co., Ltd.) 0.100 g, and buffer (NaHCO 3 ) 0.100 g in deionized water 60.00 g.
• preservative PROXEL (registered trademark) XL2(s) manufactured by LONZA Co., Ltd.
• buffer NaHCO 3
• Example 2 to 16 Aqueous additive solutions 2 to 16 (100 g each) were prepared in the same manner as in Example 1, except that the types and amounts of each component were changed to those shown in Tables 1 to 4 below.
• Example 21 100 g of an additive aqueous solution 21 was prepared in the same manner as in Example 1 except that the same ingredients as in Example 2 were used and the pH was changed to 9.0.
• Example 22 100 g of an additive aqueous solution 22 was prepared in the same manner as in Example 1 except that the same ingredients as in Example 2 were used and the pH was changed to 8.0.
• Example 23 100 g of an additive aqueous solution 23 was prepared in the same manner as in Example 1 except that the same ingredients as in Example 2 were used and the pH was changed to 7.5.
• Example 24 100 g of an additive aqueous solution 24 was prepared in the same manner as in Example 1 except that the same ingredients as in Example 2 were used and the pH was changed to 7.0.
• Example 25 100 g of an additive aqueous solution 25 was prepared in the same manner as in Example 1 except that the same ingredients as in Example 2 were used and the pH was changed to 6.5.
• Example 26 to 32 Aqueous additive solutions 26 to 32 (100 g each) were prepared in the same manner as in Example 1, except that the types and amounts of each component were changed to those shown in Tables 5 and 6 below.
• Comparative additive aqueous solutions 1 to 12 (100 g each) were prepared in the same manner as in Example 1 except that the types and amounts of each component were changed to those shown in Tables 7 to 9 below.
• ⁇ Liquid physical property change A solution that maintains the same physical properties (absorbance, viscosity, and surface tension) as each aqueous solution immediately after preparation of the additive aqueous solution. A change of 2 items or more after the compulsory test and a change of ⁇ 3% or more in the liquid property value was C, and the evaluation was made on a three-grade scale. The absorbance, viscosity, and surface tension values were measured by the following methods.
• UV-Vis spectrograph UV-1800 manufactured by Shimadzu Corporation
• 200 mg of the additive aqueous solution was weighed, diluted to 50 ml with deionized water, and further diluted to 100 mL using 2 ml of the diluent with deionized water.
• the diluted aqueous solution was injected into a 1 cm ⁇ 1 cm quartz cell, and the absorbance in the range of 250 nm to 400 nm was measured under an environment of 25° C. and relative humidity of 50%.
• the change before and after the forced test was calculated.
• ⁇ Change in pH value A indicates that the pH value remains the same as that of each aqueous solution immediately after preparation of the additive aqueous solution, B indicates that the pH value changes by ⁇ 0.3 or more after the forced test, and B indicates that the pH value changes after the forced test.
• a change of ⁇ 0.5 or more was designated as C, and evaluated on a three-grade scale.
• the pH value was measured by the following methods, respectively. After weighing 5 mL of the additive aqueous solution using a pH meter (HM-25G) manufactured by Toa DKK Co., Ltd., the measurement was performed in an environment of 25° C. and a relative humidity of 50 to 70% for 2 minutes.
• the additive aqueous solution of the example of the present invention has excellent storage stability even when the additive is contained at a high concentration.
• the content of compound (A) was 0.01 to 1.00% by mass and the content of compound (II) was 5.00 to 20.00% by mass, and a forced test was conducted for 10 weeks. It was found that the storage stability of the aqueous additive solution was very high, with no change in liquid properties even after the treatment.
• chelating agents, preservatives, and buffering agents pH value stabilizers
• Example 33 (Preparation of colorant aqueous solution 33) 0.33 parts by weight of compound (a)-1, 9.67 parts by weight of compound (P-3), 31.6 parts by weight of cyan dye (C-12), 42.2 parts by weight of cyan dye (C-26) , Cyan dye (C-47 and C-48) 21.1 parts by weight, cyan dye (C-62) 4.7 parts by weight, cyan dye (C-73) 0.4 parts by weight, chelating agent (EDTA) 1 .50 parts by mass, 1.0 parts by mass of preservative (PROXEL (registered trademark) XL2(s) manufactured by LONZA Co., Ltd.), 1.00 parts by mass of buffer (NaHCO 3 ), and 200.00 parts by mass of deionized water.
• EDTA chelating agent
• a coloring agent aqueous solution cyan dye aqueous solution
• Example 34 (Preparation of colorant aqueous solution 34) 0.33 parts by weight of compound (a)-1, 9.67 parts by weight of compound (P-3), 6.25 parts by weight of cyan dye (C-12), 25.00 parts by weight of cyan dye (C-26) , Cyan dye (C-47 and C-48) 37.50 parts by weight, cyan dye (C-62) 25.00 parts by weight, cyan dye (C-73) 6.25 parts by weight, chelating agent (EDTA) 1 .50 parts by mass, 1.00 parts by mass of preservative (PROXEL (registered trademark) XL2(s) manufactured by LONZA Co., Ltd.), 1.00 parts by mass of buffer (NaHCO 3 ), and 200.00 parts by mass of deionized water.
• EDTA chelating agent
• a colorant aqueous solution (cyan dye aqueous solution) 34 (1000 parts by mass).
• Example 35 (Preparation of colorant aqueous solution 35) 0.33 parts by weight of compound (a)-1, 9.67 parts by weight of compound (P-3), 6.06 parts by weight of cyan dye (C-12), 0.19 parts by weight of cyan dye (C-14) , Cyan dye (C-26) 24.25 parts by weight, cyan dye (C-28) 0.75 parts by weight, cyan dye (C-47 and C-48) 36.38 parts by weight, cyan dye (C-59 and C-60) 1.12 parts by mass, cyan dye (C-62) 24.25 parts by mass, cyan dye (C-69) 0.75 parts by mass, cyan dye (C-73) 6.25 parts by mass, 1.5 parts by mass of a chelating agent (EDTA), 1.00 parts by mass of a preservative (PROXEL (registered trademark) XL2(s) manufactured by LONZA), and 1.00 parts by mass of a buffer (NaHCO 3 ) were deionized.
• EDTA chelating
• a coloring agent aqueous solution (cyan dye aqueous solution) 35 (1000 parts by mass).
• Example 36 (Preparation of ink composition 36) 48.0 parts by mass of the coloring agent aqueous solution 34 prepared in Example 34, 9.70 parts by mass of glycerin, 3.40 parts by mass of triethylene glycol, 9.90 parts by mass of triethylene glycol monobutyl ether, 2-pyrrolidone2.
• Example 37 (Preparation of ink composition 37) 48.0 parts by mass of the aqueous coloring agent solution 35 prepared in Example 35, 9.70 parts by mass of glycerin, 3.40 parts by mass of triethylene glycol, 9.90 parts by mass of triethylene glycol monobutyl ether, 2-pyrrolidone2.
• Example 41 (Preparation of colorant aqueous solution 41) A coloring agent aqueous solution (black dye aqueous solution) 41 (1000 parts by mass) was prepared in the same manner as in Example 38 except that no buffer (NaHCO 3 ) was added.
• Example 42 (Preparation of colorant aqueous solution 42) Colorant aqueous solution (black dye aqueous solution) 42 (1000 parts by mass) was prepared in the same manner as in Example 38 except that no preservative (PROXEL (registered trademark) XL2(s) manufactured by LONZA Co., Ltd.) was added. was prepared.
• PROXEL registered trademark
• Example 43 (Preparation of colorant aqueous solution 43) A coloring agent aqueous solution (black dye aqueous solution) 43 (1000 parts by mass) was prepared in the same manner as in Example 38 except that no chelating agent (EDTA) was added.
• EDTA chelating agent
• Example 44 (Preparation of ink composition 44) 65.0 parts by mass of the coloring agent aqueous solution 38 prepared in Example 38, 10.0 parts by mass of glycerin, 2.0 parts by mass of triethylene glycol, 10.0 parts by mass of triethylene glycol monobutyl ether, 2-pyrrolidone2.
• Example 45 (Preparation of ink composition 45) 65.0 parts by mass of the aqueous coloring agent solution 39 prepared in Example 39, 10.0 parts by mass of glycerin, 2.0 parts by mass of triethylene glycol, 10.0 parts by mass of triethylene glycol monobutyl ether, 2-pyrrolidone2.
• ink composition (gray dye ink composition) 46 (100 parts by mass) were prepared.
• Example 47 (Preparation of ink composition 47) 65.0 parts by mass of the coloring agent aqueous solution 38 prepared in Example 38, 6.5 parts by mass of glycerin, 2.3 parts by mass of triethylene glycol, 2.9 parts by mass of 1,5-pentanediol, 2-pyrrolidone3.
• Example 48 (Preparation of ink composition 48) 65.0 parts by mass of the aqueous coloring agent solution 39 prepared in Example 39, 6.5 parts by mass of glycerin, 2.3 parts by mass of triethylene glycol, 2.9 parts by mass of 1,5-pentanediol, 2-pyrrolidone3.
• Example 49 (Preparation of ink composition 49) 8.8 parts by mass of the coloring agent aqueous solution 40 prepared in Example 40, 6.5 parts by mass of glycerin, 2.3 parts by mass of triethylene glycol, 2.9 parts by mass of 1,5-pentanediol, 2-pyrrolidone3.
• Comparative Example 17 (Preparation of comparative coloring agent aqueous solution 17) Comparative colorant aqueous solution (comparative black dye aqueous solution) 17 (1000 parts by mass) was prepared in the same manner as in Example 38 except that compound (a)-1 was not added.
• Comparative colorant aqueous solution (comparative black dye aqueous solution) 18 (1000 parts by mass) was prepared in the same manner as in Example 38 described above, except that compound (P-3) and buffer (NaHCO 3 ) were not added. .
• Comparative Example 19 (Preparation of Comparative Colorant Aqueous Solution 19) Comparative coloring agent aqueous solution (comparative black Dye aqueous solution) 19 (1000 parts by mass) was prepared.
• Comparative coloring agent aqueous solution 20 (1000 parts by mass) was prepared in the same manner as in Example 38 except that compound (P-3) and chelating agent (EDTA) were not added.
• ⁇ Storage stability of colorant aqueous solution and ink composition Aqueous coloring agent solutions 33 to 35, 38 to 43 prepared in Examples 33 to 49, ink compositions 36 to 37, 44 to 49, and comparative aqueous coloring agent solutions 17 to 20 prepared in Comparative Examples 17 to 20 were forcibly applied.
• Aqueous coloring agent solutions 33 to 35, 38 to 43 prepared in Examples 33 to 49, ink compositions 36 to 37, 44 to 49, and comparative aqueous coloring agent solutions 17 to 20 prepared in Comparative Examples 17 to 20 were forcibly applied.
• the storage stability was evaluated after storing for 4 weeks under conditions of 60°C and 50% relative humidity, after storing for 10 weeks under conditions of 60°C and 50% relative humidity, after storing for 15 weeks under conditions of 60°C and 50% relative humidity , and at 60° C. and 50% relative humidity for 20 weeks.
• aqueous coloring agent solution 450 mg (0.45 g) of the aqueous coloring agent solution was weighed using a UV-Vis spectrograph (UV-1800) manufactured by Shimadzu Corporation, diluted to 50 ml with deionized water, and then diluted. After diluting 2 ml to 100 ml with deionized water, the diluted aqueous solution was poured into a 1 cm ⁇ 1 cm quartz cell, and the absorbance in the range of 250 nm to 900 nm was measured at 25° C. and 50% relative humidity. After confirming the absorbance of ⁇ max in the ultraviolet to visible region (250 to 700 nm), the change before and after the forced test was calculated.
• UV-Vis spectrograph UV-1800
• UV-Vis spectrograph (UV-1800) manufactured by Shimadzu Corporation
• 200 mg (0.2 g) of the ink composition was weighed, diluted to 50 ml with deionized water, and further diluted with a diluted solution.
• the diluted aqueous solution was poured into a 1 cm ⁇ 1 cm quartz cell, and the absorbance in the range of 250 nm to 400 nm was measured at 25° C. and 50% relative humidity. After confirming the absorbance of ⁇ max in the ultraviolet region (250 to 300 nm), the change before and after the forced test was calculated.
• the aqueous coloring agent solutions and ink compositions of the examples of the present invention are excellent in storage stability even when the coloring agent is contained at a high concentration.
• the content of compound (A) in the aqueous coloring agent solution is 0.001 to 0.3% by mass, and the content of compound (II) is 0.5 to 8.0% by mass. It was found that the liquid physical properties did not change even after 10 weeks, and the storage stability of the colorant aqueous solution and the ink composition was very high.
• an aqueous additive solution for an ink composition, an aqueous colorant solution and an ink composition for an ink composition, an ink composition for inkjet recording containing the ink composition, and an inkjet recording method using the ink composition for inkjet recording be able to.

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