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
  • C09D11/36—Inkjet printing inks based on non-aqueous solvents
• • 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
  • C09D11/02—Printing inks
  • C09D11/10—Printing inks based on artificial resins
• • 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
  • C09D11/02—Printing inks
  • C09D11/10—Printing inks based on artificial resins
  • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
  • C09D11/104—Polyesters
• • 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
  • C09D11/02—Printing inks
  • C09D11/10—Printing inks based on artificial resins
  • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
• • 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
  • C09D11/02—Printing inks
  • C09D11/14—Printing inks based on carbohydrates
• • 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
  • C09D11/322—Pigment inks
• • 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
  • 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
  • C09D11/40—Ink-sets specially adapted for multi-colour inkjet printing

Definitions

• the present invention relates to a non-aqueous ink composition, an ink set, a recording method using the same, a method for producing a recorded matter, a recorded matter, and an inkjet recording apparatus.
• an aqueous ink composition in which a coloring material is dissolved or dispersed in water or a mixture of water and an organic solvent, or a non-aqueous ink composition in which a coloring material is dissolved or dispersed in an organic solvent that does not contain water. is widely used.
• Patent Document 1 describes an aqueous pigment containing a perinone-based pigment and an azo compound as pigments, and an aqueous ink composition for inkjet recording using the same.
• Patent Document 1 describes that the non-aqueous ink composition contains a perinone-based pigment and an azo compound, thereby having good storage stability.
• Patent Document 2 discloses a non-aqueous ink composition containing a pigment containing a diketopyrrolopyrrole pigment as a pigment, an organic solvent, and an inorganic metal, wherein the non-aqueous ink composition contains a predetermined amount of a metal element. disclosed. According to Patent Document 1, it is described that this non-aqueous ink composition has excellent chroma in the obtained recorded matter and has excellent storage stability.
• Patent Document 3 discloses an ink composition for inkjet recording containing a copper complex dye (copper phthalocyanine), wherein the concentration of free copper ions in the ink composition is 10 ppm or less.
• a copper complex dye copper phthalocyanine
• JP 2012-172070 A JP 2017-132891 A JP-A-2000-355665
• ink compositions containing perinone-based pigments are particularly suitable for producing recorded matter for outdoor use.
• the ink composition when the ink composition is ejected through an inkjet head during ejection by the inkjet method, clogging may occur in the nozzles of the inkjet head due to solid components such as resins contained in the non-aqueous ink composition.
• the inkjet recording apparatus is equipped with a cleaning recovery function that eliminates nozzle clogging in such inkjet heads.
• cleaning recoverability the ability to eliminate nozzle clogging in an inkjet head by the cleaning recovery function is referred to as cleaning recoverability.
• halogenated phthalocyanine pigments in which some of the hydrogen atoms in a pigment having a phthalocyanine structure are substituted with halogens. Halogenation of the phthalocyanine pigment results in a green pigment.
• a green ink that contains a green pigment in addition to the usual four color inks, the saturation is improved compared to the case of reproducing green with two colors of yellow ink and cyan ink. Reproducibility can be improved.
• phthalocyanine-based pigments have higher weather resistance than yellow-based pigments generally used in yellow inks. Therefore, by using a green ink containing a halogenated phthalocyanine pigment, it is possible to improve the weather resistance of a printed matter as compared with the case where two colors of yellow ink and cyan ink are used.
• non-aqueous ink compositions containing halogenated phthalocyanine pigments tend to precipitate in the non-aqueous ink composition, resulting in poor storage stability.
• a non-aqueous ink composition having poor storage stability even if an attempt is made to eliminate clogging of the nozzles in the inkjet head by the cleaning recovery function of the inkjet recording apparatus, it may not be possible to sufficiently eliminate the clogging of the nozzles. be.
• An object of the present invention is to provide a non-aqueous ink composition containing a perinone pigment that can be suitably used as a non-aqueous ink composition ejected by an inkjet method. .
• Another object of the present invention is to provide a non-aqueous ink composition that has high storage stability and high cleaning recovery even if it contains a diketopyrrolopyrrole pigment.
• Another object of the present invention is to provide a non-aqueous ink composition containing a halogenated phthalocyanine pigment that exhibits high storage stability, color tone stability, and cleaning recovery.
• the inventors of the present invention conducted intensive studies to solve the above problems, and found that the above problems can be solved by a non-aqueous ink composition containing a diketopyrrolopyrrole pigment within a predetermined pH range. The discovery led to the completion of the present invention.
• the inventors of the present invention conducted intensive studies to solve the above problems, and found that the above problems can be solved by a non-aqueous ink composition containing a halogenated phthalocyanine pigment and a predetermined organic solvent.
• the discovery led to the completion of the present invention.
• the present invention provides the following.
• the pigment contains at least one of a pigment A1 represented by the following formula (1-1) or a pigment A2 represented by the following formula (1-2),
• the pH of the pigments A1 and A2 is in the range of 3 or more and 9 or less.
• each of X1 to X12 is independently a hydrogen atom, a halogen atom, an optionally branched alkyl group having 1 to 5 carbon atoms, an optionally substituted aromatic hydrocarbon hydrogen group, cyano group, nitro group, amino group, -OH, -COOH, -COO - M + , -SO 3 H, -SO 3 - M + , phthalimido group in which hydrogen atom may be substituted, phthalimidomethyl group, or a heterocyclic compound, and M + indicates a cation.
• each of X1 to X10 is independently a hydrogen atom, a halogen atom, an optionally branched alkyl group having 1 to 5 carbon atoms, an optionally substituted aromatic hydrocarbon hydrogen group, cyano group, nitro group, amino group, -OH, -COOH, -COO - M + , -SO 3 H, -SO 3
• Organic solvent B at least one selected from the group consisting of alkylamide solvents (b1), cyclic amide solvents (b2), and lactone solvents (b3)
• Organic solvent B at least one selected from the group consisting of alkylamide solvents (b1), cyclic amide solvents (b2), and lactone solvents (b3)
• the pigment A3 according to any one of (5) to (8), wherein the pigment A3 is at least one selected from the group consisting of chlorinated phthalocyanine pigments, brominated phthalocyanine pigments, and chlorine brominated phthalocyanine pigments.
• Non-aqueous ink composition Non-aqueous ink composition.
• the alkylamide solvent (b1) contains at least one selected from the group consisting of N,N-diethylformamide, N,N-diethylpropanamide, and N,N-diethylacetamide (14 ).
• the non-aqueous ink composition according to any one of (1) to (28), which is used in an inkjet recording apparatus provided with a valve mechanism for adjusting a flow path of the non-aqueous ink composition.
• a recording method comprising ejecting the non-aqueous ink composition according to any one of (1) to (29) onto the surface of a substrate by an inkjet method.
• (31) A method for producing a recorded matter, wherein the non-aqueous ink composition according to any one of (1) to (29) is ejected onto the surface of a substrate by an inkjet method.
• An ink set comprising at least the non-aqueous ink composition according to any one of (1) to (29).
• An inkjet recording apparatus for ejecting the non-aqueous ink composition according to any one of (1) to (29) by an inkjet method, comprising a storage mechanism for storing the non-aqueous ink composition, and an inkjet ejection port. and a tube through which the non-aqueous ink composition flows, wherein the tube is connected to the storage mechanism and the inkjet ejection port, and includes a valve mechanism that adjusts the flow path of the non-aqueous ink composition.
• An inkjet recording device for ejecting the non-aqueous ink composition according to any one of (1) to (29) by an inkjet method, comprising a storage mechanism for storing the non-aqueous ink composition, and an inkjet ejection port. and a tube through which the non-aqueous ink composition flows, wherein the tube is connected to the storage mechanism and the inkjet ejection port, and includes a valve mechanism that adjusts the flow path of the non-aqueous ink composition.
• the non-aqueous ink composition of the present invention can be suitably used as a non-aqueous ink composition ejected by an inkjet method even when a pigment containing a perinone pigment is used.
• non-aqueous ink composition of the present invention has high storage stability and high cleaning recovery even when a pigment containing a diketopyrrolopyrrole pigment is used.
• non-aqueous ink composition of the present invention has high storage stability, color tone stability, and recovery from cleaning even if it contains a halogenated phthalocyanine pigment.
• a non-aqueous ink composition of one embodiment of the present invention contains a pigment, a pigment dispersant, and an organic solvent. It is a non-aqueous ink composition ejected by an inkjet method.
• non-aqueous ink composition refers to an ink composition containing an organic solvent produced without intentionally containing water, unlike an aqueous ink composition containing water as a main component. means to be a thing.
• the ink composition according to the present embodiment produces a printed matter by drying (volatilizing) the organic solvent. It is preferably an ink composition that can be obtained. Specifically, in such an ink composition, a volatile component such as an organic solvent contained in the ink composition dries (volatilizes), and the residue deposits on the surface of the substrate to form a recorded matter. do.
• This ink composition is different from an active energy ray-curable ink composition that polymerizes and cures on a substrate upon irradiation with an active energy ray such as ultraviolet rays.
• An active energy ray-curable ink composition contains a polymerizable compound as an essential component, but an ink composition capable of obtaining a recorded matter by drying (volatilizing) an organic solvent contains an organic solvent. It is not necessary to contain a polymerizable compound as an essential component, and it may contain a polymerizable compound or may not contain a polymerizable compound.
• the pigment contained in the non-aqueous ink composition contains at least one of pigment A1 represented by formula (1-1) below or pigment A2 represented by formula (1-2) below, and pigment A1 and
• the pH of A2 is characterized by being in the range of 3 or more and 9 or less.
• X1 to X12 are substituents containing hydrogen.
• X1 to X12 are each independently hydrogen, a halogen atom, an optionally branched alkyl group having 1 to 5 carbon atoms, Aromatic hydrocarbon groups optionally substituted with hydrogen atoms, cyano groups, nitro groups, amino groups, -OH, -COOH, -COO - M + , -SO 3 H, -SO 3 - M + , hydrogen atoms represents an optionally substituted phthalimido group, phthalimidomethyl group, or heterocyclic compound, and M + represents a cation.
• each of X1 to X10 is independently a hydrogen atom, a halogen atom, an optionally branched alkyl group having 1 to 5 carbon atoms, an optionally substituted aromatic hydrocarbon hydrogen group, cyano group, nitro group, amino group, -OH, -COOH, -COO - M +
• the non-aqueous ink composition of one embodiment of the present invention is a non-aqueous ink composition ejected by an inkjet method containing a pigment, a pigment dispersant, and an organic solvent.
• the pigment contained in this non-aqueous ink composition contains a halogenated phthalocyanine pigment A3, and the organic solvent contains an organic solvent B described below.
• Organic solvent B at least one selected from the group consisting of alkylamide solvents (b1), cyclic amide solvents (b2), and lactone solvents (b3)
• a non-aqueous ink composition of a first embodiment according to the present embodiment is a non-aqueous ink composition ejected by an inkjet method containing a pigment, a pigment dispersant, and an organic solvent.
• the “non-aqueous ink composition” means an ink composition containing an organic solvent produced without intentionally containing water, unlike an aqueous ink composition containing water as a main component. means.
• the pigment contained in this non-aqueous ink composition is characterized in that it contains a pigment A1 represented by the following formula (1-1), and the pH of the pigment A1 is within the range of 3 or more and 9 or less.
• X1 to X12 are substituents containing hydrogen.
• X1 to X12 are each independently hydrogen, a halogen atom, an optionally branched alkyl group having 1 to 5 carbon atoms, Aromatic hydrocarbon groups optionally substituted with hydrogen atoms, cyano groups, nitro groups, amino groups, -OH, -COOH, -COO - M + , -SO 3 H, -SO 3 - M + , hydrogen atoms represents an optionally substituted phthalimido group, phthalimidomethyl group, or heterocyclic compound, and M + represents a cation.
• the pigment A1 whose pH is controlled within the range of 3 or more and 9 or less, it is possible to suppress the aggregation of the pigments in the non-aqueous ink composition. This satisfies various properties required in a non-aqueous ink composition ejected by an inkjet method.
• Pigment A1 having a pH of 3 or more and 9 or less is treated, for example, by washing the pigment A1 with a solution (acid solution, alkaline solution, or neutral solution), or by treating the surface of the pigment with formula (1-1) It can be obtained by changing the type of substituents (X1 to X12) in the benzene ring in the structure of or by treating both.
• a method of changing the type of substituents (X1 to X12) in the benzene ring includes a method of dispersing the pigment in an organic solvent and introducing a desired substituent with an additive capable of introducing a specific substituent.
• the pH of the pigment can be adjusted by the method described in Japanese Patent No. 2993392.
• the positions at which the substituents X1 to X12 are substituted are within the range of pH 3 or more and 9 or less of the benzene ring. Any one of the 12 substitution positions is not particularly limited, and the number of substituents is also not particularly limited.
• the pH of Pigment A1 is the pH measured by the test method of JIS K5101-17-1:2004. The same applies to the method for measuring the pH of Pigment A2, which will be described later.
• the upper limit of the pH of Pigment A1 is preferably 9 or less, more preferably 8 or less, and even more preferably 7 or less.
• the lower limit of the pH of Pigment A1 is preferably 3 or higher, more preferably 5 or higher.
• the pH of the pigment A1 is 9 or less, the pigment dispersant is more likely to adhere, so aggregation of the pigment A1 in the non-aqueous ink composition can be more effectively suppressed. This can improve the ejection stability and color tone stability of the non-aqueous ink composition.
• the water content in the non-aqueous ink composition according to the present embodiment is preferably 5.0% by mass or less, preferably 1.0% by mass or less, and 0% by mass of the total amount of the non-aqueous ink composition. 0.5 mass or less is more preferable.
• Pigment A1 is highly hydrophobic, a non-aqueous inkjet composition containing this pigment tends to deteriorate dispersibility of the pigment and storage stability relatively easily due to contact with water. By reducing the water content in the non-aqueous ink composition so that it contains as little water as possible (intentionally avoiding water), storage stability, recovery from cleaning, etc. are improved. becomes possible. The same applies to non-aqueous ink compositions of second and third embodiments described later.
• the average particle size of the pigment A1 is not particularly limited, but the upper limit of the volume-based cumulative 90% particle size (D90) is preferably 500 nm or less, preferably 450 nm or less, and more preferably 400 nm. . As a result, aggregation of the pigment A1 in the non-aqueous ink composition can be more effectively suppressed, and the non-aqueous ink composition can be more preferably used as a non-aqueous ink composition ejected by an inkjet method.
• the lower limit of the volume-based cumulative 90% particle diameter (D90) is preferably 50 nm or more, more preferably 100 nm or more.
• volume-based cumulative 50% particle diameter (D50) means a particle diameter at which the cumulative volume calculated from the small diameter side is 50%.
• volume-based cumulative 50% particle size (D50) may also be referred to as “volume average particle size D50” or “median (median) size”.
• Volume-based cumulative 90% particle diameter (D90) means a particle diameter at which the cumulative volume calculated from the small diameter side is 90%.
• Volume-based cumulative 50% particle size (D50)” and “Volume-based cumulative 90% particle size (D90)” are measured using a particle size distribution measuring device (Microtrack Bell Co., Ltd. particle size analyzer NANOTRACWAVE). can be done. The same applies to non-aqueous ink compositions of second and third embodiments described later.
• the content of the pigment A1 is not particularly limited, but the lower limit of the content of the pigment A1 is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, based on the total amount of the non-aqueous ink composition. More preferably, it is 0.5% by mass or more.
• the upper limit of the content of Pigment A1 is preferably 8.0% by mass or less, more preferably 6.0% by mass or less, and even more preferably 5.0% by mass or less.
• the content of pigment A1 is 8.0% by mass or less in the total amount of the non-aqueous ink composition, it is possible to relatively increase the content of other additives, and further increase the content of pigment A1. Since it is possible to suppress an increase in viscosity due to this, it is possible to suppress clogging of the nozzles of the inkjet head.
• Pigment A1 represented by formula (1-1) may be mentioned.
• Pigment A1 represented by formula (1-1) may be synthesized, for example, commercially available C.I. I. Pigment Orange 43 is washed with a solution (acid solution, alkaline solution, or neutral solution) to treat the surface of the pigment or remove the substituent ( It may be obtained by changing the type of X1 to X12) or by performing both treatments.
• a solution as the type of X1 to X12
• Commercially available products include A-76 manufactured by Arimoto Chemical Co., Ltd., Hostaperm Orange GR and PV Gast Orange GRL manufactured by Clariant, Fasogen Super Orange 6200 manufactured by DIC, and Lionogen Orange GR-F manufactured by Toyo Ink. be done.
• non-aqueous ink composition according to the present embodiment may further contain coloring materials (including pigments and dyes) other than the pigment A1 described above.
• coloring materials include pigments and dyes of hues similar to pigment A1 (eg, orange, magenta, yellow, red).
• organic pigments other than the above-mentioned pigment A1 are exemplified by the color index (C.I.) number, C.I. I. Pigment Yellow 1, 2, 3, 12, 13, 14, 16, 17, 20, 24, 73, 74, 75, 83, 93, 95, 97, 98, 109, 110, 114, 117, 120, 125, 128, 129, 130, 137, 138, 139, 147, 148, 150, 151, 153, 154, 155, 166, 168, 180, 185, 213, 214, C.I. I.
• a dispersing aid (pigment derivative), which will be described later, may be used together with the pigment dispersant. Thereby, the dispersion stability of the pigment can be improved.
• Organic solvent is capable of dispersing or dissolving each component contained in the non-aqueous ink composition according to this embodiment.
• the organic solvent is not particularly limited, but organic solvent B (alkylamide solvent (b1), cyclic amide solvent ( b2) and at least one selected from the group consisting of a lactone solvent (b3)).
• alkylamide-based solvent (b1) the cyclic amide-based solvent (b2), and the lactone-based solvent (b3) contained in the organic solvent B are described below.
• alkylamide-based solvent those having, for example, the following structures can be preferably used.
• R 1 is hydrogen or an alkyl group having 1 to 4 carbon atoms
• R 2 and R 3 each independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms.
• R 2 and R 3 in formula (2) are preferably alkyl groups having 1 to 4 carbon atoms, and more preferably alkyl groups having 2 to 4 carbon atoms.
• alkylamide solvents include N,N-diethylformamide, N,N-diethylacetamide, N,N-dipropylformamide, N,N-dibutylformamide, N,N-diethylpropanamide, N , N-dipropylpropanamide, N-ethylformamide, N-ethylacetamide and the like.
• the content of the alkylamide solvent (b1) is not particularly limited, but the lower limit of the content of the alkylamide solvent (b1) is preferably in the range of 1% by mass or more based on the total amount of the non-aqueous ink composition.
• the range of 5% by mass or more is more preferable, and the range of 8% by mass or more is even more preferable.
• the upper limit of the content of the alkylamide solvent (b1) is preferably 90% by mass or less, more preferably 80% by mass or less, and 75% by mass or less in the total amount of the non-aqueous ink composition. More preferred.
• Cyclic amide solvent (b2) is a solvent having a cyclic structure and a —C( ⁇ O)—N— group in the cyclic structure.
• a cyclic amide solvent having, for example, the following structure can be preferably used.
• R 4 is an alkylene group having 3 to 5 carbon atoms
• R 5 represents hydrogen, an alkyl group having 1 to 4 carbon atoms, or an unsaturated hydrocarbon group.
• cyclic amide solvent (b2) examples include N-methylcaprolactam, N-acetylcaprolactam, ⁇ -caprolactam, N-vinylcaprolactam, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl- 2-pyrrolidone, N-propyl-2-pyrrolidone, N-ethyl- ⁇ -caprolactam, N-propyl- ⁇ -caprolactam, N-methyl- ⁇ -caprolactam and the like.
• the content of the cyclic amide-based solvent (b2) is not particularly limited, but the lower limit of the content of the cyclic amide-based solvent (b2) is preferably in the range of 1% by mass or more based on the total amount of the non-aqueous ink composition.
• the range of 5% by mass or more is more preferable, and the range of 8% by mass or more is even more preferable.
• the upper limit of the content of the cyclic amide solvent (b2) is preferably 90% by mass or less, more preferably 80% by mass or less, and 75% by mass or less in the total amount of the non-aqueous ink composition. More preferred.
• Lactone Solvent is a solvent having a cyclic ester structure.
• a lactone-based solvent having, for example, the following structure can be preferably used.
• R 6 is an alkylene group having 3 to 5 carbon atoms
• R 7 represents hydrogen or an alkyl group having 1 to 2 carbon atoms.
• R 6 has 4 carbon atoms.
• An alkylene group having 5 or less is more preferable, and an alkylene group having 5 carbon atoms is more preferable.
• Lactone-based solvents (b3) include ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -hexanolactone, ⁇ -caprolactone, ⁇ -valerolactone, ⁇ -hexalactone, ⁇ -heptalactone, ⁇ -octalactone, ⁇ - nonalactone, ⁇ -decalactone, ⁇ -undecalactone, ⁇ -heptalactone, ⁇ -octalactone, ⁇ -nonalactone, ⁇ -decalactone, ⁇ -undecalactone and the like.
• ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -hexanolactone, ⁇ -caprolactone and ⁇ -valerolactone are more preferable, and ⁇ -caprolactone is more preferable.
• the content of the lactone-based solvent (b3) is not particularly limited, but the lower limit of the content of the lactone-based solvent (b3) is preferably in the range of 1% by mass or more in the total amount of the non-aqueous ink composition, and 5% by mass. % or more, more preferably 8 mass % or more.
• the upper limit of the content of the lactone-based solvent (b3) is preferably 90% by mass or less, more preferably 70% by mass or less, and even more preferably 50% by mass or less in the total amount of the non-aqueous ink composition. .
• the organic solvents B "containing an alkylamide solvent (b1)” or “containing a cyclic amide solvent (b2)” is preferable, and among them, "containing an alkylamide solvent (b1) ' is more preferred.
• the pigment containing the pigment A1 can be dispersed more effectively, and the storage stability and cleaning recovery of the non-aqueous ink composition can be improved.
• the non-aqueous ink composition has a high surface drying property on the base material, resulting in less blurring of the print and clearer print.
• the organic solvent B contains at least one of the alkylamide solvent (b1), the cyclic amide solvent (b2), and the lactone solvent (b3), the effect is sufficiently exhibited.
• the lower limit of the total content of the organic solvent B is preferably in the range of 1% by mass or more, more preferably 5% by mass or more in the total amount of the non-aqueous ink composition. Preferably, it is more preferably in the range of 10% by mass or more.
• the upper limit of the total content of the organic solvent B is preferably 90% by mass or less in the total amount of the non-aqueous ink composition.
• the non-aqueous ink composition according to this embodiment may contain an organic solvent other than the organic solvent B described above.
• organic solvents include glycol ether dialkyl in which OH groups at both ends of glycol are alkyl-substituted, glycol ether monoalkyl in which OH groups on one side of glycol are alkyl-substituted, and ester carbonates.
• Glycol ether-based solvents include glycol ether dialkyl in which OH groups at both ends of glycol are alkyl-substituted, and glycol ether monoalkyl in which one OH group of glycol is alkyl-substituted.
• Glycol ether solvents include, for example, those containing at least one of glycol ether dialkyl and glycol ether monoalkyl represented by the following formula (5).
• R 8 (—OR 9 ) n —OR 10 (5)
• R 8 and R 10 are each independently hydrogen or an optionally branched alkyl group having 1 to 8 carbon atoms, and R 9 is a branched group having 1 to 4 carbon atoms. (n represents an integer of 1 or more and 6 or less).
• glycol ether solvents examples include ethylene glycol mono-n-butyl ether, ethylene glycol mono-isobutyl ether, ethylene glycol mono-t-butyl ether, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol monomethyl (or ethyl, Propyl, isopropyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl ether, triethylene glycol monomethyl (or ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl) ether, tetraethylene glycol Monomethyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-isobutyl ether, propylene glycol mono-t-butyl ether, propylene glycol mono-2-ethylhexyl
• diethylene glycol dimethyl ether diethylene glycol diethyl ether, diethylene glycol monobutyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dipropyl ether, diethylene glycol propyl methyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl methyl ether, diethylene glycol butyl ethyl ether, diethylene glycol methyl-2-ethylhexyl ether.
• triethylene glycol dimethyl ether triethylene glycol diethyl ether, triethylene glycol ethyl methyl ether, tetraethylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, propylene glycol methyl propyl ether, propylene glycol methyl butyl ether, propylene glycol methyl- 2-ethylhexyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl methyl ether, dipropylene glycol methyl propyl ether, dipropylene glycol dipropyl ether, tripropylene glycol dimethyl ether, tripropylene glycol ethyl methyl ether, etc. , are preferred.
• glycol ether solvents having different flash points it is preferable to combine two or more types of glycol ether solvents having different flash points among these glycol ether solvents.
• a glycol ether solvent with a high flash point for example, a flash point of 70° C. or higher
• a non-aqueous ink composition having high recovery from cleaning can be obtained.
• a glycol ether solvent with a low flash point for example, a flash point of less than 70° C.
• a non-aqueous ink composition with high surface drying property on a substrate can be obtained.
• glycol ether solvent may contain other solvents than the glycol ether solvent.
• carbonic acid esters such as propylene carbonate and ethylene carbonate
• oxazolidinone solvents such as 3-methyl-2-oxazolidinone, 3-ethyl-2-oxazolidinone, and N-vinylmethyloxazolidinone
• triethylene glycol butyl ether acetate and ethylene Acetate solvents such as glycol butyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol methyl ether acetate, diethylene glycol butyl ether acetate, propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, 1-methoxy-2-propyl acetate, and 3-methoxy Propanamide, 3-butoxypropanamide, N,N-dimethyl-3-methoxypropanamide, N,N-dibutyl-3-methoxypropanamide, N,
• the content of the other organic solvent is not particularly limited, but the lower limit of the content of the other organic solvent is preferably in the range of 10% by mass or more, and more preferably in the range of 20% by mass or more. , 30% by mass or more.
• the upper limit of the content of other organic solvents is preferably 85% by mass or less, more preferably 80% by mass or less, and even more preferably 75% by mass or less.
• a dispersant may be used as necessary in the non-aqueous ink composition according to the present embodiment. Any dispersant used in non-aqueous ink compositions can be used as the dispersant.
• a polymer dispersant is preferably used as the dispersant. Such a dispersant has a main chain of polyester, polyacrylic, polyurethane, polyamine, polycaprolactone, etc., and has a polar group such as an amino group, a carboxyl group, a sulfone group, or a hydroxyl group as a side chain. is.
• polyacrylic dispersants for example, Disperbyk-2000, 2001, 2008, 2009, 2010, 2020, 2020N, 2022, 2025, 2050, 2070, 2095, 2150, 2151, 2155, 2163, 2164, BYKJET-9130, 9131 , 9132, 9133, 9151 (manufactured by Vic Chemie), Efka PX4310, PX4320, PX4330, PA4401, 4402, PA4403, 4570, 7411, 7477, PX4700, PX4701 (manufactured by BASF), TREPLUS D-1200, D-1410, D-1420, MD-1000 (manufactured by Otsuka Chemical Co., Ltd.), Floren DOPA-15BHFS, 17HF, 22, G-700, 900, NC-500, GW-1500 (manufactured by Kyoeisha Chemical Co., Ltd.), and the like are used.
• Polycaprolactone-based dispersants include, for example, Ajisper PB821, PB822, PB881 (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Hinoact KF-1000, T-6000, T-7000, T-8000, T-8000E, T-9050 ( Kawaken Fine Chemicals Co., Ltd.), Solsperse 20000, 24000, 32000, 32500, 32550, 32600, 33000, 33500, 34000, 35200, 36000, 37500, 39000, 71000, 76400, 76500, 86000, 88000, J10 TEGO Dispers 652, 655, 685, 688, 690 (manufactured by Evonik Japan) and the like are used.
• the non-aqueous ink composition according to the present embodiment containing the pigment A1 having a pH of 3 or more and 9 or less it is preferable to use a pigment dispersant having a basic group among the above. Since the pH of Pigment A1 is within the range of 3 or more and 9 or less, aggregation of Pigment A1 in the non-aqueous ink composition can be more effectively suppressed by using a pigment dispersant having a basic group. can. The same applies to the later-described non-aqueous ink composition containing the pigment A2 having a pH of 3 or more and 9 or less.
• the pigment dispersant having a basic group is more likely to adhere to the surface of the pigment A1, so the aggregation of the pigment A1 in the non-aqueous ink composition is more effective. can be suppressed to
• a pigment dispersant having an amine value in the range of 20 mgKOH/g to 100 mgKOH/g and 20 mgKOH/g to 100 mgKOH/g. Aggregation of Pigment A1 in the non-aqueous ink composition can be more effectively suppressed.
• the pH of the pigment A1 is 8 or less
• the pigment dispersant having an amine value within a predetermined range is more likely to adhere to the surface of the pigment A1, so the aggregation of the pigment A1 in the non-aqueous ink composition is further effective. can be effectively suppressed.
• the content of the pigment dispersant is not particularly limited. It is more preferably 20 parts by mass or more, more preferably 20 parts by mass or more.
• the upper limit of the content of the pigment dispersant is preferably 150 parts by mass or less, more preferably 125 parts by mass or less, and 100 parts by mass or less with respect to 100 parts by mass of the pigment in the non-aqueous ink composition. It is even more preferable to have
• a dispersing aid may be used as necessary in the non-aqueous ink composition according to the present embodiment.
• the dispersing aid is adsorbed on the surface of the coloring material (pigment), and the functional group increases the affinity with the organic solvent and dispersant in the non-aqueous ink composition, thereby improving the dispersion stability.
• the pigment derivatives described above are preferable, and known pigment derivatives having functional groups such as acidic groups, basic groups, and neutral groups in the organic pigment residue can be used. The same applies to non-aqueous ink compositions of second and third embodiments described later.
• the non-aqueous ink composition according to the present embodiment may contain no resin, but may contain a resin.
• the fixability, water resistance and stretchability of the recording layer formed from the non-aqueous ink composition can be improved. Furthermore, the glossiness of the obtained recorded matter can be improved. The same applies to non-aqueous ink compositions of second and third embodiments described later.
• resins include, but are not limited to, acrylic resins, polystyrene resins, polyester resins, vinyl chloride resins, vinyl acetate resins, vinyl chloride vinyl acetate copolymer resins, polyethylene resins, polyurethane resins, and rosin-modified resins.
• Resins, acrylamide-based resins, epoxy-based resins, or copolymer resins or mixtures thereof can be used.
• those containing acrylic resins, vinyl chloride resins, cellulose resins, polyester resins, and polyurethane resins are preferable.
• the acrylic resin is not particularly limited as long as it is contained as a main component of the monomers that make up the (meth)acrylic acid ester monomer.
• the acrylic resin may be a homopolymer of one kind of radically polymerizable monomer, or may be a copolymer of two or more kinds of selected radically polymerizable monomers.
• a preferred acrylic resin for the non-aqueous ink composition according to the embodiment is a polymer of methyl methacrylate, or selected from the group consisting of methyl methacrylate, butyl methacrylate, ethoxyethyl methacrylate, and benzyl methacrylate.
• the vinyl chloride resin may be either a homopolymer composed of a vinyl chloride monomer or a copolymer using two or more selected polymerizable monomers.
• copolymers of vinyl chloride resins include vinyl chloride-vinyl acetate copolymer resins.
• a vinyl chloride-vinyl acetate copolymer resin is a polymer of vinyl chloride monomer and vinyl acetate monomer.
• Vinyl chloride-vinyl acetate copolymer resins include, for example, vinyl chloride-vinyl acetate copolymer, vinyl chloride/vinyl acetate/maleic acid copolymer, vinyl chloride/vinyl acetate/vinyl alcohol copolymer, vinyl chloride/vinyl acetate / hydroxyalkyl acrylate copolymers, etc., and mixtures thereof.
• the vinyl chloride-vinyl acetate copolymer resins include "SOLBIN C", “SOLBIN CL”, “SOLBIN CNL”, “SOLBIN CLL”, “SOLBIN CLL2", and "SOLBIN C5R" from Nissin Chemical Industry Co., Ltd. ”, “SOLBIN TA2”, “SOLBIN TA3”, “SOLBIN A”, “SOLBIN AL”, “SOLBIN TA5R”, “SOLBIN M5” and the like.
• a vinyl chloride-vinyl acetate copolymer resin can be obtained by polymerizing a vinyl chloride monomer and a vinyl acetate monomer.
• a conventionally known polymerization method may be used as the polymerization method.
• the polymerization method is preferably emulsion polymerization or suspension polymerization, more preferably suspension polymerization.
• a cellulose-based resin is a resin with a cellulose skeleton that is obtained by biologically or chemically introducing functional groups using cellulose as a raw material.
• cellulose-based resins include cellulose acetate butyrate resins, cellulose acetate propionate resins, cellulose acetate alkylate resins such as cellulose acetate propionate butyrate resins, cellulose acetate resins, nitrocellulose resins, and mixtures thereof. mentioned.
• the cellulose resins include "CAB551-0.01”, “CAB551-0.2", “CAB553-0.4", "CAB531-1", “CAB381-0.1” and “CAB381-0.1” available from EASTMAN. 5”, “CAB381-2”, “CAB381-20”, “CAP504”, “CAP482-0.5” and the like.
• a polyester resin contains at least a structural unit obtained by polycondensation of an alcohol component and a carboxylic acid component.
• the polyester-based resin may include a modified polyester-based resin.
• As the polyester resin Toyobo's "VYLON226", “VYLON270", “VYLON560”, “VYLON600”, “VYLON630”, “VYLON660”, “VYLON885", “VYLONGK250”, “VYLONGK810”, “VYLONGK890”, etc. It can be obtained and used under trade names such as “elitleUE-3200”, “elitleUE-3285", “elitleUE-3320”, “elitleUE-9800” and “elitleUE-9885” manufactured by Unitika.
• a polyurethane resin contains at least a structural unit obtained by copolymerizing an alcohol component and an isocyanate component.
• Polyurethane-based resins may include polyurethane-based resins modified with polyester, polyether, or caprolactone. Examples of the polyurethane-based resins include "Uriano KL-424", “Uriano KL-564", “Uriano KL-593", and “Uriano 3262” available from Arakawa Chemical Industries, Ltd., and "Pandex 372E” and "Uriano 372E” available from DIC.
• acrylic resins, vinyl chloride resins, cellulose resins, polyester resins, and polyurethane resins may be used alone, but it is preferable to use two of them in combination. It is more preferable to use a resin in which a resin and a vinyl chloride resin are mixed.
• the content ratio of the acrylic resin and the vinyl chloride resin can be controlled so as to meet the requirements for the non-aqueous ink composition, such as color development, drying property, coating properties, printability, and the like.
• the mixing ratio is not particularly limited and can be changed as appropriate.
• the resin contained in the non-aqueous ink composition is not particularly limited, but it is preferably contained in the range of 0.05% by mass or more, and contained in the range of 0.1% by mass or more, based on the total amount of the non-aqueous ink composition. is more preferable, and it is even more preferable to contain in the range of 0.5% by mass or more. This can further improve the surface drying property of the obtained recorded matter.
• the resin contained in the non-aqueous ink composition is preferably contained in a range of 20.0% by mass or less, more preferably 15.0% by mass or less, based on the total amount of the non-aqueous ink composition. It is more preferable to contain in the range of 10.0% by mass or less. This makes it possible to more effectively eliminate clogging in the nozzles of the inkjet head and improve the storage stability of the non-aqueous ink composition.
• the resin contained in the non-aqueous ink composition according to the present embodiment preferably has a resin having an intrinsic viscosity of 90 mL/g or more at 25°C in a range of 5% by mass or less in the total amount of the resin.
• the non-aqueous ink composition according to the present embodiment has high storage stability and high cleaning recovery by containing a perinone pigment within a predetermined pH range, and further has an intrinsic viscosity of 90 mL.
• /g or more is in the range of 5% by mass or less in the total amount of the resin, clogging in the nozzles of the inkjet head is more effectively eliminated, and the storage stability of the non-aqueous ink composition, recovery from cleaning, and Discharge stability can be significantly improved.
• the intrinsic viscosity is the specific viscosity after the target resin is dispersed in a developing solvent and the molecules contained in the resin are separated by a column filled with granular gel in GPC (gel permeation chromatography) [ ⁇ SP ](( ⁇ 0 )/ ⁇ 0 ( ⁇ 0 : solvent viscosity, ⁇ : solution viscosity)) and concentration C are calculated, and the concentration C is set to 0 in the formula Lim ([ ⁇ SP ]/C). It can be obtained by interpolation (C ⁇ 0).
• the developing solvent is not particularly limited, for example, tetrahydrofuran can be used. The same applies to non-aqueous ink compositions of second and third embodiments described later.
• the content of the resin having an intrinsic viscosity of 90 mL/g or more at 25°C is preferably in the range of 5.0% by mass or less, more preferably 4.0% by mass or less, based on the total amount of the resin.
• the range of 3.0% by mass or less is even more preferable.
• Non-aqueous ink composition for the purpose of suppressing volatilization of the non-aqueous ink composition in devices such as nozzles and tubes, preventing solidification, and resolubility when solidified,
• a surfactant for the purpose of reducing the surface tension and improving the wettability with the recording medium (substrate), for the purpose of suppressing bleeding of the ink composition on the substrate, and for improving the abrasion resistance of the coating film.
• a surfactant may be added for the purpose and for the purpose of further improving the glossiness of the recorded matter. The same applies to non-aqueous ink compositions of second and third embodiments described later.
• the surfactant preferably contains a surfactant having a siloxane skeleton.
• Pigment A1 tends to aggregate easily in a non-aqueous ink composition and tends to have a large volume average particle size. As a result, the glossiness of the obtained recorded matter may be lowered.
• a surfactant having a siloxane skeleton in the non-aqueous ink composition according to the present embodiment, it is possible to improve the glossiness of the resulting recorded matter even when the pigment A1 is included.
• a non-aqueous ink containing a surfactant having a siloxane skeleton printed matter is less likely to bleed and a recorded matter with improved abrasion resistance can be obtained.
• polyester-modified silicone or polyether-modified silicone As the surfactant having a siloxane skeleton, it is preferable to use polyester-modified silicone or polyether-modified silicone. Specific examples include BYK-313, 315N, 322, 326, 331, 347, 348, BYK-UV3500 and 3510. , 3530, 3570 (both manufactured by BYK-Chemie Japan) and the like can be used.
• the non-aqueous ink composition according to the present embodiment may contain a surfactant different from the surfactant having a siloxane skeleton.
• a surfactant different from the surfactant having a siloxane skeleton.
• Surfactants are not limited to those described above, and any of anionic, cationic, amphoteric or nonionic surfactants can be used.
• the non-aqueous ink composition according to the present embodiment may contain these surfactants together with a surfactant having a siloxane skeleton, or may contain these surfactants without containing a surfactant having a siloxane skeleton. It may contain an agent.
• the content of the surfactant is not particularly limited, but the lower limit of the content of the surfactant is preferably in the range of 0.01% by mass or more. It is preferably in the range of 0.05% by mass or more, more preferably in the range of 0.1% by mass or more.
• the lower limit of the surfactant content is preferably 5.0% by mass or less, more preferably 4.0% by mass or less, and 3.0% by mass or less. is more preferred.
• the non-aqueous ink composition according to the present embodiment includes stabilizers such as antioxidants and ultraviolet absorbers, epoxides and the like, polyvalent carboxylic acids, surface conditioners, leveling agents (acrylic, silicone, etc.), and erasers.
• stabilizers such as antioxidants and ultraviolet absorbers, epoxides and the like, polyvalent carboxylic acids, surface conditioners, leveling agents (acrylic, silicone, etc.), and erasers.
• Known additives such as foaming agents, pH adjusters, bactericides, preservatives, deodorants, charge control agents, and wetting agents may be included as optional components.
• Specific examples of antioxidants include hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, hydrazine-based antioxidants, and the like.
• Specific examples include BHA (2,3-butyl-4-oxyanisole) and BHT (2,6-di-t-butyl-p-cresol).
• a benzophenone-based compound or a benzotriazole-based compound can be used as the ultraviolet absorber.
• Specific examples of the epoxidized product include epoxy glyceride, epoxy fatty acid monoester, and epoxy hexahydrophthalate, and specific examples include ADEKA CIZER O-130P and ADEKA CIZER O-180A (manufactured by ADEKA). exemplified.
• Specific examples of polycarboxylic acids include citric acid and maleic acid.
• a non-aqueous ink composition according to a second embodiment of the present invention is a non-aqueous ink composition ejected by an inkjet method containing a pigment, a pigment dispersant, and an organic solvent.
• the pigment contained in this non-aqueous ink composition is characterized in that it contains a pigment A2 represented by the following formula (1-2), and the pH of the pigment A2 is within the range of 3 or more and 9 or less.
• each of X1 to X10 is independently a hydrogen atom, a halogen atom, an optionally branched alkyl group having 1 to 5 carbon atoms, an optionally substituted aromatic hydrocarbon hydrogen group, cyano group, nitro group, amino group, -OH, -COOH, -COO - M + , -SO 3 H, -SO 3 - M + , phthalimido group in which hydrogen atom may be substituted, phthalimidomethyl group, or a heterocyclic compound, and M + indicates a cation.
• the pigment A2 whose pH is controlled within the range of 3 or more and 9 or less, it is possible to suppress the aggregation of the pigments in the non-aqueous ink composition, and it is possible to improve the storage stability and cleaning recovery property. .
• Pigment A2 with a pH of 3 or more and 9 or less is washed with a solution in the same manner as Pigment A1 described above, to treat the surface of the pigment, or to remove a substituent in the benzene ring in the structure of formula (1-2) It can be obtained by changing the types of (X1 to X10), or by performing both treatments.
• the method for changing the type of substituents (X1 to X10) in the benzene ring is the same as for Pigment A1 described above.
• the positions at which the substituents X1 to X10 are substituted are not particularly limited as long as the pH of the pigment A2 is within the range of 3 or more and 9 or less, and any of the 10 substitution positions on the benzene ring may be used. is not particularly limited.
• the upper limit of the pH of Pigment A2 is preferably 9 or less, more preferably 8 or less, even more preferably 7 or less, and even more preferably 6 or less.
• the lower limit of the pH of Pigment A2 is preferably 3 or higher, more preferably 4 or higher.
• the pH of the pigment A2 is 9 or less, the pigment dispersant is more likely to adhere, so aggregation of the pigment A2 in the non-aqueous ink composition can be more effectively suppressed. This can improve the ejection stability and color tone stability of the non-aqueous ink composition.
• the preferable range of the water content and the average particle size of the pigment A2 in the non-aqueous ink composition according to the present embodiment is the same as the preferable range of the water content and the pigment It is the same as the preferred range of the average particle size of A1.
• the preferred range of the content of the pigment A2 contained in the non-aqueous ink composition according to the present embodiment is the same as the preferred range of the content of the pigment A1 in the non-aqueous ink composition of the first embodiment described above. .
• the content of the pigment A2 is 8.0% by mass or less in the total amount of the non-aqueous ink composition, aggregation of the pigment A2 in the non-aqueous ink composition can be more effectively suppressed.
• pigment A2 represented by formula (1-2) C.I. I. Pigment Red 254, C.I. I. Pigment Red 255, C.I. I. Pigment Red 264, C.I. I. Pigment Red 270, C.I. I. Pigment Red 272, C.I. I. Pigment Red 283, C.I. I. Pigment Red 291, C.I. I. Pigment Orange 71, C.I. I. Pigment Orange 73, C.I. I. Pigment Orange 81 etc. can be mentioned.
• the pigment A2 represented by formula (1-2) may be synthesized, for example, by washing a commercially available diketopyrrolopyrrole pigment with a solution (acid solution, alkaline solution, or neutral solution). obtained by treating the surface of the pigment, changing the type of substituents (X1 to X10) in the benzene ring in the structure of formula (1-2), or performing both treatments.
• a solution acid solution, alkaline solution, or neutral solution
• may Commercially available products include IRGAPHR RED BT-CF manufactured by BASF, CROMOPHTAL DPP Red BP (both C.I. Pigment Red 254), Chromofine Red 6156EC manufactured by Dainichiseika Kogyo Co., Ltd. (both C.I. Pigment Red 254), Pigment Red 254 (C.I.
• Pigment Red 254 manufactured by Tokyo Chemical Industry Co., Ltd., Cinilex DPP Red SR-2P (C.I. Pigment Red 254) manufactured by CINIC, CROMOPHTAL DPP ORANGE manufactured by BASF TR, IRAGIN ORANGE D2905, (C.I. Pigment Orange 71), BASF's Irgazin Orange L 2990 HD (C.I. Pigment Orange 73), and the like.
• the non-aqueous ink composition according to the present embodiment may further contain coloring materials (including pigments and dyes) other than the pigment A2 described above.
• coloring materials include pigments and dyes of hues similar to pigment A2 (eg, orange, magenta, yellow, red).
• C.I. color index
• a dispersing aid (pigment derivative), which will be described later, may be used together with the pigment dispersant. Thereby, the dispersion stability of the pigment can be improved.
• Organic solvent is capable of dispersing or dissolving each component contained in the non-aqueous ink composition according to this embodiment.
• the organic solvent is not particularly limited, but organic solvent B (alkylamide solvent (b1), cyclic amide solvent ( b2) and at least one selected from the group consisting of a lactone solvent (b3)).
• the affinity between the glycol ether solvent and “pigment A2” is poor, so pigment A2 aggregates in the non-aqueous ink composition, resulting in recovery from cleaning. sexuality may worsen. Therefore, by including organic solvent B (at least one selected from the group consisting of alkylamide solvent (b1), cyclic amide solvent (b2), and lactone solvent (b3)), pigment A2 aggregates. It is possible to effectively suppress the deterioration of the cleaning recoverability due to this. Therefore, the organic solvent contained in the non-aqueous ink composition of the present invention is not particularly limited. By containing at least one selected from the group consisting of the solvent (b1), the cyclic amide solvent (b2), and the lactone solvent (b3), the non-aqueous solvent has high storage stability and high cleaning recovery. It becomes an ink composition.
• Preferred types of solvents in the alkylamide-based solvent (b1), the cyclic amide-based solvent (b2), and the lactone-based solvent (b3) are the alkylamide-based solvent (b1) in the non-aqueous ink composition of the first embodiment described above. , cyclic amide solvent (b2), and lactone solvent (b3).
• the content of the cyclic amide-based solvent (b2) is not particularly limited, but the lower limit of the content of the cyclic amide-based solvent (b2) is preferably in the range of 1% by mass or more based on the total amount of the non-aqueous ink composition.
• the range of 10% by mass or more is more preferable, and the range of 15% by mass or more is even more preferable.
• the content ranges are the same as those of the alkylamide solvent (b1), the cyclic amide solvent (b2), and the lactone solvent (b3) in the non-aqueous ink composition of the first embodiment.
• organic solvents B "containing an alkylamide solvent (b1)” or “containing a cyclic amide solvent (b2)” is preferable, and among them, "containing an alkylamide solvent (b1) ' is more preferred.
• the organic solvent B contains at least one of the alkylamide solvent (b1), the cyclic amide solvent (b2), and the lactone solvent (b3), the effect is sufficiently exhibited. You may mix two or more types from. When two or more organic solvents B are mixed, the preferred range of the total content of the organic solvents B contained in the non-aqueous ink composition is the same as for the non-aqueous ink composition of the first embodiment described above.
• the non-aqueous ink composition according to this embodiment may contain an organic solvent other than the organic solvent B described above.
• organic solvent other than the organic solvent B described above.
• glycol ether dialkyl in which the OH groups at both ends of the glycol are alkyl-substituted
• glycol ether monoalkyl in which one OH group of the glycol is alkyl-substituted, carbonate esters, and other solvents
• oxazolidinone-based solvents, acetate-based Solvents, amide-based solvents different from alkylamide-based solvents (b1) and cyclic amide-based solvents (b2) alkyl alcohols, ketones or keto-alcohols, ethers, oxyethylene or oxypropylene copolymers, diols, 4 alcohols, alkanolamines, etc.
• Preferred types of other organic solvents are the same as the glycol ether dialkyl, glycol ether monoalkyl, and carbonate in the non-aqueous ink composition of the first embodiment described above.
• the preferred range of the total content of other organic solvents contained in the non-aqueous ink composition is the same as for the non-aqueous ink composition of the first embodiment described above.
• a dispersant may be used as necessary in the non-aqueous ink composition according to the present embodiment.
• a preferred type of pigment dispersant is the same as the pigment dispersant in the non-aqueous ink composition of the first embodiment described above.
• the non-aqueous ink composition according to the present embodiment containing the pigment A2 having a pH of 3 or more and 9 or less it is preferable to use a pigment dispersant having a basic group among the above.
• a pigment dispersant having an amine value in the range of 20 mgKOH/g or more and 100 mgKOH/g or less it is preferable to use a pigment dispersant having an amine value in the range of 20 mgKOH/g or more and 100 mgKOH/g or less.
• the preferred range of the content of the pigment dispersant contained in the non-aqueous ink composition is the same as for the non-aqueous ink composition of the first embodiment described above.
• a dispersing aid may be used as necessary in the non-aqueous ink composition according to the present embodiment.
• the non-aqueous ink composition according to the present embodiment may contain no resin, but may contain a resin.
• Preferred resin types are the same as the resins in the non-aqueous ink composition of the first embodiment described above.
• the content of the resin contained in the non-aqueous ink composition and the preferred range of the resin having an intrinsic viscosity of 90 mL/g or more at 5° C. are the same as those of the non-aqueous ink composition of the first embodiment.
• a surfactant may be added to the non-aqueous ink composition according to the present embodiment.
• surfactants include polyoxyalkylene alkyl ethers such as nonionic P-208, P-210, P-213, E-202S, E-205S, E-215, K-204, K-220, S -207, S-215, A-10R, A-13P, NC-203, NC-207 (manufactured by NOF Corporation), Emulgen 106, 108, 707, 709, A-90, A-60 (Kao ( Co., Ltd.), Floren G-70, D-90, TG-740W (Kyoeisha Chemical Co., Ltd.), Poem J-0081HV (Riken Vitamin Co., Ltd.), Adekatol NP-620, NP-650, NP- 660, NP-675, NP-683, NP-686, Adekacol CS-141E, TS-230E (manufactured by Adeka Co., Ltd.), Solgen 30V, 40, TW-20, TW-80, Neugen C
• a fluorine-modified polymer such as Ichi Kogyo Seiyaku Co., Ltd.
• a specific example is BYK-340 (manufactured by BYK-Chemie Japan), a silicon-based silicone having a siloxane skeleton.
• the surfactant it is preferable to use polyester-modified silicone or polyether-modified silicone.
• acetylene glycol-based surfactants include Surfynol (registered trademark) 82, 104, 465, 485, TG (all manufactured by Air Products Japan), Olfin (registered trademark) STG, E1010 (both manufactured by Nissin Kagaku Co., Ltd.), and the like.
• the surfactant is not limited to the above, and any anionic, cationic, amphoteric or nonionic surfactant can be used.
• the surfactant preferably contains a surfactant having a siloxane skeleton.
• a non-aqueous ink containing a surfactant having a siloxane skeleton can reduce print bleeding and provide a recorded matter with improved abrasion resistance. The same applies to the non-aqueous ink composition of the third embodiment which will be described later.
• the content range of the surfactant contained in the non-aqueous ink composition is the same as that of the non-aqueous ink composition of the first embodiment described above.
• the non-aqueous ink composition according to this embodiment may optionally contain other components.
• the types of other components contained in the non-aqueous ink composition are the same as those of the non-aqueous ink composition of the first embodiment described above.
• Non-Aqueous Ink Composition of Third Embodiment>> is a non-aqueous ink composition that contains a pigment, a pigment dispersant, and an organic solvent and is ejected by an inkjet method.
• the pigment contained in this non-aqueous ink composition is characterized by containing the halogenated phthalocyanine pigment A3, and the organic solvent contains the following organic solvent B.
• Organic solvent B at least one selected from the group consisting of alkylamide solvents (b1), cyclic amide solvents (b2), and lactone solvents (b3)
• the halogenated phthalocyanine pigment A3 is a compound in which at least part of the hydrogen atoms on the benzene ring in the phthalocyanine skeleton are substituted with halogen atoms (fluorine, chlorine, bromine, iodine).
• X1 to X16 each independently represent a halogen atom or a hydrogen atom.
• M represents two hydrogen atoms or a metal atom which may have a ligand.
• a halogenated phthalocyanine pigment is a pigment having a structure in which a maximum of 16 halogen atoms are bonded per phthalocyanine molecule.
• phthalocyanine pigments generally have higher weather resistance than yellow pigments. For this reason, by using a green ink containing a halogenated phthalocyanine pigment, the weather resistance of the obtained recorded matter is improved compared to the case of using a yellow pigment and a blue pigment as in the methods (II) and (III). can be improved.
• the halogenated phthalocyanine pigment A3 is substituted with a halogen element, the overall density of the pigment (weight per unit volume) is high, and it is difficult to disperse it in a non-aqueous ink composition for a long period of time. Become. Therefore, when a non-aqueous ink composition containing a halogenated phthalocyanine pigment is stored for a long period of time, the pigment precipitates in the non-aqueous ink composition, resulting in deterioration of storage stability, color tone stability, and recovery from cleaning. was clarified by the research of the present inventors.
• an organic solvent B at least one selected from the group consisting of an alkylamide solvent (b1), a cyclic amide solvent (b2), and a lactone solvent (b3)
• an organic solvent B at least one selected from the group consisting of an alkylamide solvent (b1), a cyclic amide solvent (b2), and a lactone solvent (b3)
• storage stability and Color tone stability and recovery from cleaning can be improved.
• the preferred range of water content in the non-aqueous ink composition according to the present embodiment is the same as the preferred range of water content in the non-aqueous ink composition of the first embodiment described above. Since the pigment A3 is highly hydrophobic, a non-aqueous inkjet composition containing this pigment tends to deteriorate dispersibility of the pigment relatively easily due to contact with water, and storage stability tends to deteriorate. In addition to containing the organic solvent B, by reducing the water content in the non-aqueous ink composition so that it contains as little water as possible (intentionally avoiding water), halogen Precipitation of the phthalocyanine pigment A3 can be more effectively suppressed, and storage stability and ejection stability can be more effectively improved.
• the pigment contained in the non-aqueous ink composition according to this embodiment contains the halogenated phthalocyanine pigment A3.
• Halogenated phthalocyanine pigment A3 is a compound having a phthalocyanine skeleton represented by the following formula.
• X1 to X16 each independently represent a halogen atom or a hydrogen atom.
• M represents two hydrogen atoms or a metal atom which may have a ligand.
• a halogenated phthalocyanine pigment is one in which at least one of X1 to X16 is replaced with a halogen atom. That is, the halogenated phthalocyanine pigment is a pigment having a structure in which at least one halogen atom is bonded to one phthalocyanine molecule and at most 16 halogen atoms are bonded in total per phthalocyanine molecule.
• a halogenated phthalocyanine pigment having a larger number of halogen groups is more greenish.
• the number of halogen atoms substituted in the halogenated phthalocyanine pigment is preferably 1 or more, more preferably 8 or more, more preferably 12 or more, and more preferably 14 or more in order to exhibit a green hue.
• the halogenated phthalocyanine pigment A3 may have two hydrogen atoms at the center M of the phthalocyanine skeleton, or may be a halogenated metal phthalocyanine pigment in which M is a metal atom.
• M is a metal atom
• the type of metal is not particularly limited, but manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), or aluminum ( Al) is particularly desirable.
• M may have a ligand.
• Halogenated phthalocyanine pigment A3 includes C.I. I. Pigment Green 7, 36, 58, 59, 62, 63 and the like.
• Halogenated phthalocyanine pigment A3 may be produced by a conventionally known method, such as FASTGEN GREEN 2YK (C.I. Pigment Green 36) manufactured by DIC, Cyanine Green 5370 (C Pigment Green 36), FASTGEN GREEN 5740 (C.I. Pigment Green 7) manufactured by DIC, Fastogen GREEN A110 (C.I. Pigment Green 58) manufactured by DIC, and the like. .
• the volume-based cumulative 50% particle diameter (D50) of Pigment A3 is not particularly limited, but the lower limit of the volume-based cumulative 50% particle diameter (D50) is preferably 30 nm or more, more preferably 40 nm or more. More preferably, it is 50 nm or more. This improves the weather resistance of the halogenated phthalocyanine pigment A3.
• the upper limit of the volume-based cumulative 50% particle diameter (D50) is preferably 150 nm or less, more preferably 140 nm or less, and even more preferably 130 nm or less. This makes it possible to more effectively suppress the precipitation of the halogenated phthalocyanine pigment A3 in the non-aqueous ink composition, thereby improving the color tone stability.
• the volume-based cumulative 90% particle size (D90) of Pigment A3 is not particularly limited, but the lower limit of the volume-based cumulative 90% particle size (D90) is preferably 50 nm or more, more preferably 60 nm or more. , 70 nm or more. This improves the weather resistance of the halogenated phthalocyanine pigment A3.
• the upper limit of the volume-based cumulative 90% particle diameter (D90) is preferably 300 nm or less, more preferably 290 nm or less, and even more preferably 280 nm or less. This makes it possible to more effectively suppress the precipitation of the halogenated phthalocyanine pigment A3 in the non-aqueous ink composition, thereby improving the color tone stability.
• the content of pigment A3 is not particularly limited, but the lower limit of the content of pigment A3 is preferably 0.5% by mass or more, and preferably 1.0% by mass or more, based on the total amount of the non-aqueous ink composition. More preferably, it is 1.5% by mass or more. As a result, the print density becomes sufficient, and the color reproducibility of the recorded matter can be improved.
• the upper limit of the content of Pigment A3 is preferably 8.0% by mass or less, more preferably 6.0% by mass or less, and 5.0% by mass or less in the total amount of the non-aqueous ink composition. is more preferred.
• the non-aqueous ink composition according to the present embodiment may further contain coloring materials (including pigments and dyes) other than the above-described halogenated phthalocyanine pigment A3.
• coloring materials include pigments and dyes having similar skeletons and hues (cyan, green, yellow) to the halogenated phthalocyanine pigment A3.
• C.I. color index
• a dispersing aid (pigment derivative), which will be described later, may be used together with the pigment dispersant.
• the dispersion stability of the pigment can be improved, and the storage stability of the non-aqueous ink composition can be improved.
• Organic solvent is capable of dispersing or dissolving each component contained in the non-aqueous ink composition according to this embodiment.
• the organic solvent contains organic solvent B (at least one selected from the group consisting of alkylamide solvent (b1), cyclic amide solvent (b2), and lactone solvent (b3)).
• the alkylamide solvent (b1) by containing the alkylamide solvent (b1), it becomes possible to disperse the halogenated phthalocyanine pigment A3 in the non-aqueous ink composition for a long period of time, and the storage stability and color tone stability are improved. , and cleaning recoverability can be improved.
• the affinity with the pigment dispersant for dispersing the halogenated phthalocyanine pigment A3 is improved, and it is possible to effectively disperse it in a non-aqueous ink composition containing an alkylamide solvent. This is probably because the precipitation of the halogenated phthalocyanine pigment A3 can be suppressed.
• the inclusion of the cyclic amide solvent (b2) or the lactone solvent (b3) makes it possible to disperse the halogenated phthalocyanine pigment A3 in the non-aqueous ink composition for a long period of time. It was found that storage stability, color tone stability, and recovery from cleaning can be improved.
• Preferred types of solvents in the alkylamide-based solvent (b1), the cyclic amide-based solvent (b2), and the lactone-based solvent (b3) are the alkylamide-based solvent (b1) in the non-aqueous ink composition of the first embodiment described above. , cyclic amide solvent (b2), and lactone solvent (b3).
• organic solvents B "containing an alkylamide solvent (b1)” or “containing a cyclic amide solvent (b2)” is preferable, and among them, "containing an alkylamide solvent (b1) ' is more preferred.
• the organic solvent B contains at least one of the alkylamide solvent (b1), the cyclic amide solvent (b2), and the lactone solvent (b3), the effect is sufficiently exhibited. You may mix two or more types from. When two or more organic solvents B are mixed, the preferred range of the total content of the organic solvents B contained in the non-aqueous ink composition is the same as for the non-aqueous ink composition of the first embodiment described above.
• the non-aqueous ink composition according to this embodiment may contain an organic solvent other than the organic solvent B described above.
• organic solvent other than the organic solvent B described above.
• glycol ether dialkyl in which the OH groups at both ends of the glycol are alkyl-substituted
• glycol ether monoalkyl in which one OH group of the glycol is alkyl-substituted, carbonate esters, and other solvents
• oxazolidinone-based solvents, acetate-based Solvents, amide solvents different from alkylamide solvents (b1) and cyclic amide solvents (b2), alkyl alcohols, ketones or ketoalcohols, ethers, oxyethylene or oxypropylene copolymers, diols, 4 alcohols, alkanolamines, etc. oxazolidinone-based solvents, acetate-based Solvents, amide solvents different from alkylamide solvents (b1) and cyclic
• Preferred types of other organic solvents are the same as the glycol ether dialkyl, glycol ether monoalkyl, and carbonate in the non-aqueous ink composition of the first embodiment described above.
• the preferred range of the total content of other organic solvents contained in the non-aqueous ink composition is the same as for the non-aqueous ink composition of the first embodiment described above.
• a pigment dispersant may be used as necessary in the non-aqueous ink composition according to the present embodiment.
• a pigment dispersant having a basic group aggregation of the halogenated phthalocyanine pigment A3 in the non-aqueous ink composition can be more effectively suppressed.
• a preferred type of pigment dispersant is the same as the pigment dispersant in the non-aqueous ink composition of the first embodiment described above.
• a pigment dispersant having an amine value in the range of 20 mgKOH/g or more and 100 mgKOH/g or less. Aggregation of Pigment A3 in the non-aqueous ink composition can be more effectively suppressed.
• the preferred range of the content of the pigment dispersant contained in the non-aqueous ink composition is the same as for the non-aqueous ink composition of the first embodiment described above.
• a dispersing aid may be used as necessary in the non-aqueous ink composition according to the present embodiment.
• the non-aqueous ink composition according to the present embodiment may contain no resin, but may contain a resin.
• Preferred resin types are the same as the resins in the non-aqueous ink composition of the first embodiment described above.
• the preferred range of the content of the resin contained in the non-aqueous ink composition is the same as for the non-aqueous ink composition of the first embodiment described above.
• the resin contained in the non-aqueous ink composition according to the present embodiment preferably has a resin having an intrinsic viscosity of 90 mL/g or more at 25°C in a range of 5% by mass or less in the total amount of the resin.
• the content of the resin having an intrinsic viscosity of 90 mL/g or more at 25° C. is preferably 4.0% by mass or less, more preferably 3.5% by mass or less, more preferably 2.5% by mass, based on the total amount of the resin. % or less is even more preferable.
• a surfactant may be added to the non-aqueous ink composition according to the present embodiment.
• Preferred types of surfactants are the same as the surfactants in the non-aqueous ink composition of the second embodiment described above.
• the preferred range of the content of the surfactant contained in the non-aqueous ink composition is the same as for the non-aqueous ink composition of the second embodiment described above.
• the non-aqueous ink composition according to this embodiment may optionally contain other components.
• the types of other components contained in the non-aqueous ink composition are the same as in the non-aqueous ink composition of the first embodiment described above.
• the non-aqueous ink composition according to the present embodiment is produced by mixing an organic solvent, a pigment containing pigment A1 or A2, and other components (for example, a resin) using a paint shaker. can be done. At this time, each component may be dispersed with zirconia beads. Moreover, the obtained non-aqueous ink composition may be adjusted to a desired dissolved oxygen content and dissolved nitrogen content by performing a degassing treatment or the like, if necessary.
• a pigment containing pigment A3, at least 1) a pigment containing the halogenated phthalocyanine pigment A3, and other components (for example, a resin) are mixed using a paint shaker.
• the non-aqueous ink composition according to the present embodiment is a non-aqueous ink composition that does not intentionally contain water. And moisture may be mixed in during the manufacturing process. It is desirable that the water content in the non-aqueous ink composition is as low as possible. Excessive water content deteriorates storage stability and dischargeability, and further increases the risk of generation of solid components and the like.
• the upper limit of the water content in the non-aqueous ink composition is preferably 5.0% by mass or less, more preferably 1.0% by mass or less, and 0.5% by mass in the total amount of the non-aqueous ink composition. The following are particularly preferred.
• the organic solvent in advance.
• the amount of water contained in the non-aqueous composition can be reduced.
• a method for drying the organic solvent for example, a method of spraying an inert gas (e.g., nitrogen gas) dried in an inert gas atmosphere such as nitrogen for a predetermined time, a method of distilling and refining the organic solvent, and water are selected. Examples include a method of allowing the organic solvent to permeate through a semi-permeable membrane that selectively permeates the organic solvent, and a method of selectively adsorbing water mixed in the organic solvent with a water adsorbent that adsorbs water.
• an inert gas e.g., nitrogen gas
• the recording method according to the present embodiment is a recording method in which the above non-aqueous ink composition is ejected onto the surface of a substrate by an inkjet method.
• the non-aqueous ink compositions of the first and second embodiments include pigment A1 in which the substituent in the structure is changed so that the pH is in the range of 3 or more and 9 or less, or By containing A2, it satisfies the properties required for the non-aqueous ink composition ejected by the inkjet method. It satisfies the properties required for objects.
• the non-aqueous ink composition of the third embodiment has high storage stability and color tone stability even if it contains the halogenated phthalocyanine pigment A3.
• the recorded matter obtained by using the recording method also has high color tone stability.
• a method of ejecting ink by an inkjet method may be a piezo method using a piezoelectric element or a thermal method using a heating element, and is not particularly limited.
• a recording method using the above ink composition can also be defined as a method for producing a recorded matter.
• the non-aqueous ink composition of the first embodiment among the above non-aqueous ink compositions to produce a recorded matter, the characteristics required for a non-aqueous ink composition ejected by an inkjet method were satisfied.
• a record can be produced in the state.
• the characteristics of high storage stability and high recovery from cleaning are satisfied. Records can be produced.
• a recorded matter using the non-aqueous ink composition of the third embodiment among the above non-aqueous ink compositions a recorded matter having high color tone stability can be obtained.
• the base material (recording medium) that can be used in the recording method according to the present embodiment is not particularly limited.
• Various substrates can be used, including absorbent substrates such as fabrics, and substrates with a surface coating such as substrates having a receiving layer.
• the non-aqueous ink composition is a non-aqueous ink composition that does not contain water, it is preferable that the surface is mainly made of a resin.
• the non-aqueous ink composition contains an alkylamide-based solvent (b) that is permeable to a resin base material, bleeding of printing on a medium (recording medium) whose surface is made of a resin is reduced. and the print becomes clear.
• resins include polyvinyl chloride-based polymers, acryl, PET, polycarbonate, PE, and PP. Further, it may be used for a resin base material (so-called resin base material for lamination) that assumes lamination of a film to the recording surface of a recorded matter.
• a base material (recording medium) whose surface is made of a hard or soft polyvinyl chloride polymer is preferred.
• the substrate (recording medium) whose surface is made of a polyvinyl chloride polymer include polyvinyl chloride substrates (films or sheets).
• the recording layer (also referred to as printing layer) is a layer formed by volatilization of the solvent contained in the non-aqueous ink composition, and forms a desired image.
• the non-aqueous ink composition of the first embodiment among the above non-aqueous ink compositions, the properties required for the non-aqueous ink composition ejected by the inkjet method are satisfied.
• the non-aqueous ink composition of the second embodiment has high storage stability and high recovery from cleaning. A desired image can be formed.
• the non-aqueous ink composition of the third embodiment By ejecting the non-aqueous ink composition of the third embodiment among the above non-aqueous ink compositions, a recording layer having high color tone stability can be obtained. Moreover, since the above non-aqueous ink composition has high storage stability, it is possible to form a desired image even with a non-aqueous ink composition that has been stored for a long period of time.
• the recorded matter according to this embodiment may further include a layer having a desired function on the upper surface of the recording layer (printing layer).
• a layer having a desired function on the upper surface of the recording layer may be formed for the purpose of further imparting abrasion resistance and glossiness to the recorded matter.
• a layer having a textured surface may be formed by adding a filler or changing the film thickness for each pixel.
• a weather-resistant layer containing an ultraviolet absorber, a light stabilizer, etc., a glittering layer containing a glittering pigment, or the like may be formed.
• the ink set according to the present embodiment is an ink set comprising at least the above non-aqueous ink composition.
• the above non-aqueous ink composition is a red ink, an orange ink or a green ink
• the effect of the present invention can be obtained by combining the conventionally known yellow ink, magenta ink, cyan ink and black ink. In addition to performance, it is possible to expand color reproducibility.
• an ink set containing the above non-aqueous ink composition and a glittering ink such as white ink, metallic ink, or pearl ink, or an ink set containing clear ink containing no pigment may be used.
• Inkjet recording device A conventionally known inkjet recording apparatus that ejects the above non-aqueous ink composition by an inkjet method can be used.
• an inkjet printer such as VersaArt RE-640 manufactured by Roland DG Co., etc. can be used.
• an on-carriage type and serial printer type inkjet recording apparatus will be described. It may be an off-carriage type inkjet recording device fixed to the head, or a line printer type inkjet recording device in which the ink composition is ejected onto the recording medium (substrate) without moving the inkjet head. good.
• the inkjet recording apparatus preferably includes a heating mechanism and a fixing mechanism for fixing the substrate.
• the organic solvent contained in the non-aqueous ink composition is dried by controlling the substrate surface temperature with a heating mechanism provided in the inkjet recording apparatus and drying the non-aqueous ink composition that has landed on the substrate (recording medium). can be volatilized.
• the fixing mechanism for fixing the base material makes it possible to dry the non-aqueous ink composition while the base material (recording medium) is fixed. Uniformity can be suppressed. This makes it possible to effectively dry the non-aqueous ink composition that has landed on the substrate (recording medium).
• the heating mechanism provided in the inkjet recording apparatus may be a pre-heater, a platen heater, an after-heater, or the like, or may be a mechanism for blowing warm air onto the recorded matter. Also, a plurality of these heating mechanisms may be combined.
• the surface temperature of the substrate heated by the heating mechanism is not particularly limited as long as the organic solvent contained in the non-aqueous ink composition can be volatilized, and the lower limit of the surface temperature of the substrate is 20° C. or higher. , more preferably 30° C. or higher, and even more preferably 40° C. or higher.
• the upper limit of the surface temperature of the substrate is preferably 70° C. or lower, more preferably 60° C. or lower, and even more preferably 50° C. or lower.
• the fixing mechanism for fixing the base material may be a fixing mechanism that fixes the base material with a predetermined jig, or a fixing mechanism that sucks and adsorbs the base material using negative pressure, and is not particularly limited.
• the inkjet head that ejects the above non-aqueous ink composition may be a piezo inkjet head using a piezoelectric element or a thermal inkjet head using a heating element, and is not particularly limited.
• a container for storing the non-aqueous ink composition is connected to an inkjet ejection port for ejecting the non-aqueous ink composition, and the non-aqueous ink composition is applied.
• a circulating plastic tube may be provided, and the above non-aqueous ink composition may be supplied to the inkjet head through the plastic tube and ejected by an inkjet method.
• the inkjet recording apparatus preferably has a mechanism capable of eliminating nozzle clogging.
• the effect of the present invention can be more effectively achieved by providing a mechanism capable of eliminating nozzle clogging.
• the tube connected to the storage mechanism and the inkjet ejection port has a valve mechanism that adjusts the flow path of the non-aqueous ink composition.
• the ejection stability of the non-aqueous ink composition can be further improved by supplying the non-aqueous ink composition from the storage mechanism to the inkjet ejection port via the valve mechanism.
• the material of the plastic tube is not particularly limited, but includes polyolefin resin such as polyethylene resin, ethylene propylene diene rubber, nylon, polyurethane, PTFE, and the like. Among these, polyethylene resins and ethylene propylene diene rubbers are preferred.
• the ink jet recording apparatus can be used for each color ink such as yellow, magenta, cyan, and black, as well as for light magenta, light cyan, light black, orange, green, red, and white, as described above.
• the inkjet recording apparatus may or may not have a winding mechanism for the recording medium (base material), a drying mechanism for drying the surface of the base material, and an ink circulation mechanism.
• (First embodiment) Preparation of resin (1) Acrylic resin In 300 g of diethylene glycol diethyl ether kept at 100 ° C., 150 g of methyl methacrylate and 50 g of butyl methacrylate and a predetermined amount of t-butyl peroxy-2-ethylhexanoate (polymerization initiation agent) was added dropwise over 1.5 hours. After completion of the dropwise addition, the mixture was allowed to react at 100° C. for 2 hours and then cooled to obtain a colorless and transparent polymer solution of methyl methacrylate. Thereafter, the solvent was sufficiently distilled off from this polymer solution to obtain a polymer of methyl methacrylate.
• polymerization initiation agent t-butyl peroxy-2-ethylhexanoate
• the amount of t-butylperoxy-2-ethylhexanoate which is a polymerization initiator, was changed to control the polymerization average molecular weight of methyl methacrylate (acrylic resin) to be 30,000 to 105,000 (this The mass of the polymerization initiator used is shown in the following Table 1. In Table 1, it is described as "initiator amount").
• Polyester-based resin 104 parts by mass of terephthalic acid, 104 parts by mass of isophthalic acid, 79 parts by mass of ethylene glycol, 89 parts by mass of neopentyl glycol, and 0.1 part by mass of tetrabutyl titanate were placed in a round-bottomed flask and allowed to cool for 4 hours. The temperature was gradually raised to 240° C., and the esterification reaction was carried out while removing the distillate out of the system. After completion of the esterification reaction, the pressure was reduced to 10 mmHg over 30 minutes, and the temperature was raised to 250° C. for initial polymerization. After that, post-polymerization was carried out at 1 mmHg or less for 1 hour to obtain a polyester resin.
• PPAXEL CD-220 manufactured by Daicel
• IPDI isophorone diisocyanate
• DEF N,N-diethylformamide
• Table 1 shows the weight average molecular weight (relative molecular mass) of each resin (acrylic resin, vinyl chloride-vinyl acetate copolymer resin, cellulose resin, polyester resin, polyurethane resin), and the intrinsic viscosity at 25 ° C. is 90 mL. / g or more resin ratio.
• the weight average molecular weight (relative molecular mass) was measured by GPC (gel permeation chromatography).
• the ratio of resins with an intrinsic viscosity of 90 mL / g or more is determined by connecting a viscosity detector (ViscoStar III manufactured by WYATT) and a refractive index detector (Optilab T-rEX manufactured by WYATT) to a Shimadzu SEC (GPC) system, Using tetrahydrofuran as a developing solvent, the sample was first passed through a column heated to 40°C in the Shimadzu SEC ( GPC ) system, and then cooled to 25°C. Then, the concentration C was determined by a refractive index detector, and the intrinsic viscosity was determined by extrapolating the concentration C to 0 in Lim ([ ⁇ SP ]/C).
• Pigment A1 Synthetic products 1 to 6 of pigment A1 were synthesized under the conditions shown in Table 2. Specifically, 2 parts by mass of the perinone pigment of (a1) in Table 2 was dispersed in the solvent of (a2) in Table 2, and (a3) in Table 2 was added ((a4) in Table 2. Table After stirring for the time (a6) in Table 2 under the temperature conditions of (a5) in 2, the synthetic products 1 and 2 were washed with ethanol, and the synthetic products 3, 4 and 6 were washed with water and the synthetic products 1 to 6 of the pigment A1.
• Pigment Ap (synthetic product 5) in Table 2 is a pigment synthesized by the method described in Japanese Patent No. 3076738 and is pigment A1 represented by formula (1-1). was not dispersed in a solvent.
• the pH of synthetic products 1 to 6 of Pigment A1 was measured according to the test method of JIS K5101-17-1:2004 (described in (a7) of Table 2).
• Non-aqueous ink compositions of Examples and Comparative Examples were prepared according to the proportions of each component shown in the table below. Specifically, each component was dispersed with zirconia beads using a paint shaker to prepare a non-aqueous ink composition. The unit is % by mass. The particle size and dispersion time of the zirconia beads are shown in Tables 3 to 10 below.
• volume-based cumulative 90% particle size (D90) of the pigment contained in the non-aqueous ink composition was measured using a particle size distribution analyzer (particle size analyzer NANOTRACWAVE manufactured by Microtrack Bell Co., Ltd.).
• Evaluation 2 Either the change rate of the viscosity or the volume-based cumulative 50% particle diameter (D50) of the pigment is 8% or more and less than 10%.
• Evaluation 1 Either the change rate of the viscosity or the volume-based cumulative 50% particle diameter (D50) of the pigment is 10% or more.
• Ejection stability was evaluated for the non-aqueous ink compositions of Examples, Comparative Examples, and Reference Examples. Specifically, an inkjet printer (trade name: VersaArt RE-640, manufactured by Roland DG Co., Ltd.) is filled with a non-aqueous ink composition, and a recording medium (polyvinyl chloride film with glue (IMAGin JT5829R: MACtac Co., Ltd.) is used. )) in a bi-directional high-speed printing mode (360 x 720 dpi), solid and fine lines are printed by continuous printing at a substrate surface temperature of 40 ° C, and the presence or absence of missing dots, flight deflection, and ink splattering is visually observed.
• a recording medium polyvinyl chloride film with glue (IMAGin JT5829R: MACtac Co., Ltd.)
• a bi-directional high-speed printing mode 360 x 720 dpi
• Evaluation Criteria Evaluation 5 Within the 24-hour test period, dot missing, flight deflection, or ink scattering occurred less than 10 times. Evaluation 4: During the test period of 24 hours, dot missing, flight deflection, or ink scattering occurred 10 times or more and less than 20 times. Evaluation 3: During the test period of 24 hours, dot missing, flight deflection, or ink scattering occurred 20 times or more and less than 30 times. Evaluation 2: During the test period of 24 hours, dot missing, flight deflection, or ink scattering occurred 30 times or more and less than 40 times. Evaluation 1: During the test period of 24 hours, dot missing, flight deflection, or ink scattering occurred 40 times or more.
• Solid filling was evaluated for the non-aqueous ink compositions of Examples, Comparative Examples, and Reference Examples. Specifically, with the inkjet printer (trade name: VersaArt RE-640, manufactured by Roland DG Co., Ltd.), a recording medium (polyvinyl chloride film with glue (IMAGin JT5829R: manufactured by MACtac)) was printed bidirectionally. Printing was carried out at a substrate surface temperature of 40° C. in a high-speed printing mode (360 ⁇ 720 dpi), and filling (blank spots) of the solid printed portion was confirmed (denoted as “solid filling” in the table).
• a recording medium polyvinyl chloride film with glue (IMAGin JT5829R: manufactured by MACtac)
• Evaluation 5 A uniform solid image is formed
• Evaluation 4 White spots cannot be visually confirmed, but slight color unevenness can be confirmed, but the design is not impaired
• Evaluation 3 White spots cannot be visually confirmed, Color unevenness can be observed.
• Evaluation 2 White spots can be observed.
• Evaluation 1 White spots can be observed remarkably, and a decrease in density is observed.
• the non-aqueous ink compositions of Examples, Comparative Examples and Reference Examples were evaluated for surface drying properties. Specifically, the non-aqueous ink compositions of Examples and Comparative Examples were applied to a recording medium (adhesive polychlorinated A solid image was printed on a vinyl film (IMAGin JT5829R: manufactured by MACtac) in a high-quality print mode (1440 x 720 dpi), and the time taken to dry at 40°C was measured (referred to as "surface dryness" in the table). . Rating Criteria Rating 5: Dries in less than 2 minutes. Evaluation 4: Dry in 2 minutes or more and less than 4 minutes. Evaluation 3: Dry in 4 minutes or more and less than 6 minutes. Evaluation 2: Dry in 6 minutes or more and less than 8 minutes. Evaluation 1: It dries in 8 minutes or more.
• the non-aqueous ink compositions of Examples and Comparative Examples were evaluated for color development. Specifically, high-quality printing is performed on a recording medium (polyvinyl chloride film with glue (IMAGin JT5829R: manufactured by MACtac)) using the inkjet printer (trade name: VersaArt RE-640, manufactured by Roland DG Co., Ltd.). A solid image was printed in mode (1440 ⁇ 720 dpi). The chroma was measured based on JIS Z 8721 using X-Rite eXact (manufactured by X-Rite) under the conditions of a viewing angle of 2°, a measurement range of 4 mm ⁇ , and a D65 light source.
• a recording medium polyvinyl chloride film with glue (IMAGin JT5829R: manufactured by MACtac)
• the inkjet printer (trade name: VersaArt RE-640, manufactured by Roland DG Co., Ltd.).
• a solid image was printed in mode (1440
• Evaluation Criteria Evaluation 5 Saturation is 100 or more.
• Evaluation 4 Saturation is 90 or more and less than 100.
• Evaluation 3 Saturation is 80 or more and less than 90.
• Evaluation 2 Saturation is 70 or more and less than 80.
• Evaluation 1 Saturation is less than 70.
• the weather resistance of prints produced using the non-aqueous ink compositions of Examples, Comparative Examples and Reference Examples was evaluated.
• the non-aqueous ink compositions of Examples and Comparative Examples were applied to a recording medium (polyvinyl chloride film with glue (IMAGin JT5829R (manufactured by MACtac)) was printed with a solid image in a high-quality print mode (1440 ⁇ 720 dpi) and dried at 40° C. for 1 hour.
• the recorded matter thus obtained was put into a xenon weather meter (ATLAS Ci4000: manufactured by Toyo Seiki Co., Ltd.) and subjected to a cycle test.
• Test conditions are based on JIS K-5600-7-7, black panel temperature: 63°C, xenon lamp irradiance: 60W/m 2 , temperature inside test layer: 38°C, and humidity in segment 1 is 50%. 102 minutes in a state of maintaining at 200° C., and 18 minutes of water irradiation in segment 2, which was regarded as one cycle. With 50 cycles as one set, this cycle test was continued for 10 sets. The value of hue change ⁇ E before and after the test was evaluated, and the hue was evaluated under the following conditions.
• Evaluation 4 ⁇ E is less than 20.0 and 10.0 or more.
• Evaluation 3 ⁇ E is less than 30.0 and 20.0 or more.
• Glossiness Glossiness was evaluated for the non-aqueous ink compositions of Examples, Comparative Examples and Reference Examples. Specifically, the non-aqueous ink compositions of Examples and Comparative Examples were applied to a recording medium (glued poly Print a solid part on a vinyl chloride film (IMAGin JT5829R: manufactured by MACtac) in a high-quality print mode (1440 x 720 dpi) at a substrate surface temperature of 40 ° C. After drying for 5 minutes in an oven at 60 ° C., the printed matter was measured for 20° gloss.
• a recording medium glued poly Print a solid part on a vinyl chloride film (IMAGin JT5829R: manufactured by MACtac) in a high-quality print mode (1440 x 720 dpi) at a substrate surface temperature of 40 ° C. After drying for 5 minutes in an oven at 60 ° C., the printed matter was measured for 20° gloss.
• the values of L * , a * , and b * were measured under the conditions of a viewing angle of 2°, a measurement range of 4 mm ⁇ , and a D65 light source (in the table, "color tone stability (sedimentation gender)”).
• the hue change ⁇ E is determined by the following formula using the values of L *1 , a *1 , b *1 before the test and L *2 , a *2 , b *2 after the test.
• ⁇ E ((L * 1 - L * 2 ) 2 + (a * 1 - a * 2 ) 2 + (b * 1 - b * 2 ) 2 ) (1/2) Evaluation Criteria Evaluation 5: ⁇ E is less than 2.0. Evaluation 4: ⁇ E is less than 2.5 and 2.0 or more. Evaluation 3: ⁇ E is less than 3.0 and 2.5 or more. Evaluation 2: ⁇ E is less than 3.5 and 3.0 or more. Evaluation 1: ⁇ E is 3.5 or more.
• the The water-based ink composition had good storage stability as compared with Examples 1-13.
• the non-aqueous ink compositions of Examples 1-14 to 1-30 and 1-72 to 1-75 in which the content of the resin having an intrinsic viscosity of 90 mL/g or more at 25°C was changed the intrinsic viscosity at 25°C Compared to the non-aqueous ink compositions of Examples in which the amount of the resin having a viscosity of 90 mL/g or more is 5% by mass or less based on the total amount of the resin, Solid filling and intermittent ejection have been improved.
• the organic solvent B (at least one selected from the group consisting of an alkylamide solvent (b1), a cyclic amide solvent (b2), and a lactone solvent (b3)) of Example 1-1 containing
• the aqueous ink composition has various properties required for a non-aqueous ink composition ejected by an inkjet method even when compared with the non-aqueous ink compositions of Examples 1-31 to 1-33 that do not contain the organic solvent B. was better.
• Example 1-34 to 1-41 in which the content of the organic solvent B was changed, Examples 1-34 to 1-40 in which the content of the organic solvent B was in the range of 1% by mass to 90% by mass
• the non-aqueous ink composition of Example 1-41 has better color development and weather resistance than the non-aqueous ink composition of Example 1-41, and various properties required for non-aqueous ink compositions ejected by the inkjet method. The characteristics were better.
• the various properties required for the non-aqueous ink composition ejected by the inkjet method are also better, and the organic solvent B (alkylamide solvent (b1), cyclic amide solvent ( A non-aqueous ink composition containing b2) and at least one selected from the group consisting of a lactone-based solvent (b3) would exhibit the effects of the present invention particularly effectively.
• Example 1-52 to 1-55 in which the content of pigment A1 was changed, the content of pigment A1 was 0.1% by mass or more and 8.0% by mass or less based on the total amount of the non-aqueous ink composition.
• the non-aqueous ink compositions of Examples 1-52 to 1-54 had better storage stability than that of Example 1-55, which is required for non-aqueous ink compositions ejected by an inkjet method. It can be seen that various properties are better.
• Example 1-60 to 1-65 in which the type of pigment dispersant was changed, the non-aqueous ink compositions of Examples 1-61 to 1-65 using a pigment dispersant having a basic group were Even compared with the non-aqueous ink composition of Example 60, the ejection stability was improved.
• the non-aqueous ink compositions of Examples 1-62 to 1-64 having an amine value in the range of 20 mgKOH/g or more and 100 mgKOH/g or less showed particularly improved ejection stability.
• Example 1-66 to 1-69 in which the content of the pigment dispersant was changed, the range of 5 parts by mass to 150 parts by mass with respect to 100 parts by mass of the pigment in the non-aqueous ink composition
• the ink compositions of Examples 1-66 to 1-68 had improved color development evaluation and surface drying property even when compared with the non-aqueous ink composition of Example 1-69.
• Example 1-1 the ink compositions of Examples 1-70 and 1-71, which did not contain a surfactant having a siloxane skeleton, had lower glossiness than the ink composition of Example 1-1.
• the non-aqueous ink composition of Comparative Example 1-1 which contains the pigment A1 having a pH of less than 3, has poor storage stability and solid filling. However, it does not satisfy the various characteristics that are required.
• the non-aqueous ink composition of Comparative Example 1-2 which contains the pigment A1 having a pH of more than 9, has deteriorated storage stability and ejection stability, and is suitable for non-aqueous ink compositions ejected by an inkjet method. It does not meet the various required properties.
• C.I. I. Pigment Orange 31 C.I. I. Reference Examples 1-1 and 1-2 containing Pigment 64 satisfy the properties required for non-aqueous ink compositions ejected by an inkjet method, and are easily aggregated in non-aqueous ink compositions. It was confirmed that this is a problem unique to non-aqueous ink compositions containing perinone pigments.
• the amount of t-butylperoxy-2-ethylhexanoate which is a polymerization initiator, was changed to control the polymerization average molecular weight of methyl methacrylate (acrylic resin) to be 30,000 to 105,000 (this The mass of the polymerization initiator used at that time is shown in Table 11 below, which is indicated as "initiator amount" in Table 11.).
• Polyester-based resin 104 parts by mass of terephthalic acid, 104 parts by mass of isophthalic acid, 79 parts by mass of ethylene glycol, 89 parts by mass of neopentyl glycol, and 0.1 part by mass of tetrabutyl titanate were placed in a round-bottomed flask and allowed to cool for 4 hours. The temperature was gradually raised to 240° C., and the esterification reaction was carried out while removing the distillate out of the system. After completion of the esterification reaction, the pressure was reduced to 10 mmHg over 30 minutes, and the temperature was raised to 250° C. for initial polymerization. After that, post-polymerization was carried out at 1 mmHg or less for 1 hour to obtain a polyester resin.
• PVAXEL CD-220 manufactured by Daicel
• IPDI isophorone diisocyanate
• DEF N,N-diethylformamide
• a prepolymer with a 250 parts by mass of N,N-diethylformamide (DEF) was added thereto and dissolved uniformly.
• a chain extender solution dissolved in 100 parts by mass of DEF) was added, and the mixture was further stirred at 60°C for 40 minutes.
• 3.8 parts of monoisopropanolamine (MIPA: manufactured by Daicel) dissolved in 50 parts by mass of N,N-diethylformamide (DEF) was added as a reaction terminator, and finally 250 parts of N,N-diethylformamide (DEF) was added. Parts by mass were added to obtain a polyurethane solution having a solid content of 25.0% by mass.
• Table 11 shows the weight average molecular weight (relative molecular mass) of each resin (acrylic resin, vinyl chloride-vinyl acetate copolymer resin, cellulose resin, polyester resin, polyurethane resin), and the intrinsic viscosity at 25 ° C. is 90 mL. / g or more resin ratio.
• the weight average molecular weight (relative molecular mass) was measured by GPC (gel permeation chromatography).
• the ratio of resins with an intrinsic viscosity of 90 mL / g or more is determined by connecting a viscosity detector (ViscoStar III manufactured by WYATT) and a refractive index detector (Optilab T-rEX manufactured by WYATT) to a Shimadzu SEC (GPC) system, Using tetrahydrofuran as a developing solvent, the sample was first passed through a column heated to 40°C in the Shimadzu SEC ( GPC ) system, and then cooled to 25°C. Then, the concentration C was determined by a refractive index detector, and the intrinsic viscosity was determined by extrapolating the concentration C to 0 in Lim ([ ⁇ SP ]/C).
• Synthetic products 1 to 3 of pigment A2 were synthesized under the conditions shown in Table 12. Specifically, 2 parts by mass of the diketopyrrolopyrrole pigment of (a8) in Table 12 was dispersed in the solvent of (a9) in Table 12, and (a10) in Table 12 was added in parts (a11) of Table 12. After stirring for the time (a13) in Table 12 under the temperature conditions of (a12) in Table 12, the mixture was washed with water to obtain Synthetic Products 1, 2 and 3 of Pigment A2.
• the pH of synthetic products 1, 2, and 3 of pigment A2 was measured according to the test method of JIS K5101-17-1:2004 ((a14) in Table 12).
• Non-aqueous ink compositions of Examples and Comparative Examples were prepared according to the proportions of each component shown in the table below. Specifically, each component was dispersed with zirconia beads using a paint shaker to prepare a non-aqueous ink composition. The unit is % by mass. The particle size and dispersion time of the zirconia beads are shown in Tables 13 to 20 below.
• volume-based cumulative 90% particle size (D90) of the pigment contained in the non-aqueous ink composition was measured using a particle size distribution analyzer (particle size analyzer NANOTRACWAVE manufactured by Microtrack Bell Co., Ltd.).
• Storage stability was evaluated for the non-aqueous ink compositions of Examples, Comparative Examples, and Reference Examples. Specifically, the non-aqueous ink composition was stored at 60° C. for one month, and changes in viscosity and volume-based cumulative 50% particle size (D50) of the pigment before and after the test were observed. evaluated the sex. The viscosity of the ink is measured at 20°C using a falling ball viscometer (AMVn manufactured by Anton Paar). It was measured at 25° C. using a particle size analyzer (NANOTRACWAVE manufactured by Microtrack Bell Co., Ltd.).
• Evaluation 2 Either the change rate of the viscosity or the volume-based cumulative 50% particle diameter (D50) of the pigment is 8% or more and less than 10%.
• Evaluation 1 Either the change rate of the viscosity or the volume-based cumulative 50% particle diameter (D50) of the pigment is 10% or more.
• Ejection stability was evaluated for the non-aqueous ink compositions of Examples, Comparative Examples, and Reference Examples. Specifically, an inkjet printer (trade name: VersaArt RE-640, manufactured by Roland DG Co., Ltd.) is filled with a non-aqueous ink composition, and a recording medium (polyvinyl chloride film with glue (IMAGin JT5829R: MACtac Co., Ltd.) is used. )) in a bi-directional high-speed printing mode (360 x 720 dpi), solid and fine lines are printed by continuous printing at a substrate surface temperature of 40 ° C, and the presence or absence of missing dots, flight deflection, and ink splattering is visually observed.
• a recording medium polyvinyl chloride film with glue (IMAGin JT5829R: MACtac Co., Ltd.)
• a bi-directional high-speed printing mode 360 x 720 dpi
• Evaluation Criteria Evaluation 5 Within the 24-hour test period, dot missing, flight deflection, or ink scattering occurred less than 10 times. Evaluation 4: During the test period of 24 hours, dot missing, flight deflection, or ink scattering occurred 10 times or more and less than 20 times. Evaluation 3: During the test period of 24 hours, dot missing, flight deflection, or ink scattering occurred 20 times or more and less than 30 times. Evaluation 2: During the test period of 24 hours, dot missing, flight deflection, or ink scattering occurred 30 times or more and less than 40 times. Evaluation 1: During the test period of 24 hours, dot missing, flight deflection, or ink scattering occurred 40 times or more. "
• Solid filling was evaluated for the non-aqueous ink compositions of Examples, Comparative Examples, and Reference Examples. Specifically, with the inkjet printer (trade name: VersaArt RE-640, manufactured by Roland DG Co., Ltd.), a recording medium (polyvinyl chloride film with glue (IMAGin JT5829R: manufactured by MACtac)) was printed bidirectionally. Printing was carried out at a substrate surface temperature of 40° C. in a high-speed printing mode (360 ⁇ 720 dpi), and filling (blank spots) of the solid printed portion was confirmed (denoted as “solid filling” in the table).
• a recording medium polyvinyl chloride film with glue (IMAGin JT5829R: manufactured by MACtac)
• Evaluation Criteria Evaluation 5 A uniform solid image is formed Evaluation 4: White spots cannot be visually confirmed, but slight color unevenness can be confirmed, but the design is not impaired Evaluation 3: White spots cannot be visually confirmed However, color unevenness can be observed. Evaluation 2: White spots can be observed. Evaluation 1: White spots can be observed remarkably, and a decrease in density is observed. "
• the non-aqueous ink compositions of Examples, Comparative Examples and Reference Examples were evaluated for surface drying properties. Specifically, the non-aqueous ink compositions of Examples and Comparative Examples were applied to a recording medium (adhesive polychlorinated A solid image was printed on a vinyl film (IMAGin JT5829R: manufactured by MACtac) in a high-quality print mode (1440 x 720 dpi), and the time taken to dry at 40°C was measured (referred to as "surface dryness" in the table). . Rating Criteria Rating 5: Dries in less than 2 minutes. Evaluation 4: Dry in 2 minutes or more and less than 4 minutes. Evaluation 3: Dry in 4 minutes or more and less than 6 minutes. Evaluation 2: Dry in 6 minutes or more and less than 8 minutes. Evaluation 1: It dries in 8 minutes or more.
• Evaluation Criteria Evaluation 5 No bleeding of ink was observed with a loupe. Evaluation 4: No bleeding of the ink was visually observed, and 6 pt characters were clear. Evaluation 3: Slight bleeding of the ink was visually observed, but the design was not damaged. Evaluation 2: Bleeding of the ink was visually observed, but the 6pt characters were recognizable. Evaluation 1: Remarkable bleeding of the ink was visually observed, and 6 pt characters were not visually recognized.
• the non-aqueous ink compositions of Examples, Comparative Examples and Reference Examples were evaluated for abrasion resistance of coating films. Specifically, the non-aqueous ink compositions of Examples and Comparative Examples were applied to a recording medium (adhesive polychlorinated A solid image was printed on a vinyl film (IMAGin JT5829R: manufactured by MACtac) in a high quality print mode (1440 ⁇ 720 dpi) and dried at 40°C. The printed surface of the printed matter was rubbed with a piece of test cloth under a load of 200 g for 50 reciprocations, and the abrasion resistance was visually evaluated.
• a recording medium adheresive polychlorinated
• IMAGin JT5829R manufactured by MACtac
• Evaluation Criteria Evaluation 5 The ink film was not peeled off, and no ink adhered to the test cloth.
• Evaluation 4 The ink film was not peeled off, but ink adhered to the test cloth.
• Evaluation 3 The ink film was slightly peeled off, and the ink film adhered to the test cloth.
• Evaluation 2 The ink film was slightly peeled off, and the ink film adhered to the test cloth.
• Evaluation 1 Most of the ink film was peeled off, and the ink film adhered to the test cloth.
• the weather resistance of prints produced using the non-aqueous ink compositions of Examples, Comparative Examples and Reference Examples was evaluated.
• the non-aqueous ink compositions of Examples and Comparative Examples were applied to a recording medium (polyvinyl chloride film with adhesive (IMAGin JT5829R (manufactured by MACtac)) was printed with a solid image in a high-quality print mode (1440 ⁇ 720 dpi) and dried at 40° C. for 1 hour.
• the recorded matter thus obtained was placed in a xenon weather meter (ATLAS Ci4000: manufactured by Toyo Seiki Co., Ltd.) and subjected to a cycle test.
• Test conditions are based on JIS K-5600-7-7, black panel temperature: 63°C, xenon lamp irradiance: 60W/m 2 , test layer temperature: 38°C, and segment 1 humidity is 50%. 102 minutes in a state of maintaining at 200° C., and 18 minutes of water irradiation in segment 2, which was regarded as one cycle. With 50 cycles as one set, this cycle test was continued for 10 sets. The value of hue change ⁇ E before and after the test was evaluated, and the hue was evaluated under the following conditions.
• Evaluation 3 ⁇ E is less than 30.0 and 20.0 or more.
• the The water-based ink composition had good storage stability even when compared with Examples 9 and 12.
• the resin having an intrinsic viscosity of 90 mL/g or more at 25°C in which the content of the resin having an intrinsic viscosity of 90 mL/g or more at 25°C was changed, the resin having an intrinsic viscosity of 90 mL/g or more at 25°C
• the non-aqueous ink compositions of Examples in the range of 5% by mass or less based on the total amount of the resin have improved solid filling and intermittent ejection properties compared to the non-aqueous ink compositions of Examples in the range of more than 5% by mass. Was.
• organic solvent B (at least one selected from the group consisting of alkylamide solvent (b1), cyclic amide solvent (b2), and lactone solvent (b3)) of Example 2-1
• organic solvent B at least one selected from the group consisting of alkylamide solvent (b1), cyclic amide solvent (b2), and lactone solvent (b3)
• the aqueous ink composition has high storage stability and recovery from cleaning, and the effect of the present invention is particularly effective. It can be seen that the
• Example 2-33 to 2-40 in which the content of the organic solvent B was changed, Examples 2-33 to 2-39 in which the content of the organic solvent B was in the range of 1% by mass or more and 90% by mass or less
• the non-aqueous ink composition of Example 2-40 has higher storage stability and recovery from cleaning than the non-aqueous ink composition of Example 2-40, and it can be seen that the effects of the present invention are exhibited particularly effectively.
• the various properties required for the non-aqueous ink composition ejected by the inkjet method are also better, and the organic solvent B (alkylamide solvent (b1), cyclic amide solvent ( b2) and at least one selected from the group consisting of a lactone solvent (b3)), the effects of the present invention are particularly effective.
• Example 2-51 to 2-54 in which the content of pigment A2 was changed, the content of pigment A2 was 0.1% by mass or more and 8.0% by mass or less based on the total amount of the non-aqueous ink composition.
• the non-aqueous ink compositions of Examples 2-51 to 2-53 had better storage stability than that of Example 2-54.
• Examples 2-59 to 2-64 and 2-70 in which the type of pigment dispersant was changed Examples 2-60 to 2-64 and 2-70 in which a pigment dispersant having a basic group was used
• the non-aqueous ink composition of Example 2-60 had improved ejection stability even when compared with the non-aqueous ink composition of Example 2-60.
• the non-aqueous ink compositions of Examples 2-60 to 2-63 having an amine value in the range of 20 mgKOH/g or more and 100 mgKOH/g or less showed particularly improved ejection stability.
• Example 2-65 to 2-68 in which the content of the pigment dispersant was changed, the range of 5 parts by mass to 150 parts by mass with respect to 100 parts by mass of the pigment in the non-aqueous ink composition
• the ink compositions of Examples 2-65 to 2-67 had improved surface drying properties and abrasion resistance of the coating film compared to the ink composition of Example 2-68.
• Example 2-69 which did not contain a surfactant having a siloxane skeleton, had a relatively slightly reduced paint film abrasion resistance.
• C.I. I. Pigment Red 149, C.I. I. Reference Examples 2-1 and 2-2 containing Pigment Red 188 satisfy the properties required for a non-aqueous ink composition ejected by an inkjet method, and easily aggregate in the non-aqueous ink composition. is a problem unique to non-aqueous ink compositions containing diketopyrrolopyrrole pigments.
• the amount of t-butylperoxy-2-ethylhexanoate which is a polymerization initiator, was changed to control the polymerization average molecular weight of methyl methacrylate (acrylic resin) to be 30,000 to 105,000 (this The mass of the polymerization initiator used at that time is shown in Table 1 below, which is indicated as "initiator amount" in Table 21).
• Polyester-based resin 104 parts by mass of terephthalic acid, 104 parts by mass of isophthalic acid, 79 parts by mass of ethylene glycol, 89 parts by mass of neopentyl glycol, and 0.1 part by mass of tetrabutyl titanate were charged into a round-bottom flask, and 240 parts by mass were added over 4 hours.
• the temperature was gradually raised to °C, and the esterification reaction was carried out while removing the distillate out of the system. After completion of the esterification reaction, the pressure was reduced to 10 mmHg over 30 minutes, and the temperature was raised to 250° C. for initial polymerization. After that, post-polymerization was carried out at 1 mmHg or less for 1 hour to obtain a polyester resin.
• PPAXEL CD-220 manufactured by Daicel
• IPDI isophorone diisocyanate
• DEF N,N-diethylformamide
• N,N-diethylformamide (DEF) was added to this and dissolving it uniformly.
• 12 parts by mass of 3-aminomethyl-3,5,5-trimethylcyclohexylamine (IPD: manufactured by Evonik) was dissolved in 100 parts by mass of DEF.
• the elongation agent solution was added and stirred at 60° C. for an additional 40 minutes.
• a reaction terminator in which 3.8 parts by mass of monoisopropanolamine (MIPA: manufactured by Daicel) is dissolved in 50 parts by mass of N,N-diethylformamide (DEF) is added, and finally N,N-diethylformamide (DEF) is added.
• MIPA monoisopropanolamine
• DEF N,N-diethylformamide
• Table 21 shows the weight average molecular weight (relative molecular mass) of each resin (acrylic resin, vinyl chloride-vinyl acetate copolymer resin, cellulose resin, polyester resin, polyurethane resin) and the intrinsic viscosity at 25 ° C. of 90 mL. / g or more resin ratio.
• the weight average molecular weight (relative molecular mass) was measured by GPC (gel permeation chromatography).
• the ratio of the resin with an intrinsic viscosity of 90 mL / g or more is determined by connecting a viscosity detector (ViscoStar III manufactured by WYATT) and a refractive index detector (Optilab T-rEX manufactured by WYATT) to a Shimadzu SEC (GPC) system, Using tetrahydrofuran as a developing solvent, the sample was first passed through a column heated to 40°C in the Shimadzu SEC (GPC) system, and then cooled to 25°C. ⁇ SP ] was determined, the concentration C was determined by a refractive index detector, and the intrinsic viscosity was determined by extrapolating the concentration C to 0 in Lim ([ ⁇ SP ]/C).
• Non-aqueous ink compositions of Examples and Comparative Examples were prepared according to the proportions of each component shown in the table below. Specifically, each component was dispersed with zirconia beads using a paint shaker to prepare a non-aqueous ink composition. The unit is % by mass. The particle size and dispersion time of the zirconia beads are shown in Tables 22 to 29 below.
• volume-based cumulative 90% particle size (D90) of the pigment contained in the non-aqueous ink composition was measured using a particle size distribution analyzer (particle size analyzer NANOTRACWAVE manufactured by Microtrack Bell Co., Ltd.).
• Storage stability was evaluated for the non-aqueous ink compositions of Examples, Comparative Examples, and Reference Examples. Specifically, the non-aqueous ink composition was stored at 60° C. for one month, and changes in viscosity and volume-based cumulative 50% particle size (D50) of the pigment before and after the test were observed. evaluated the sex. The viscosity of the ink is measured at 20°C using a falling ball viscometer (AMVn manufactured by Anton Paar). It was measured at 25° C. using a particle size analyzer (NANOTRACWAVE manufactured by Microtrack Bell Co., Ltd.).
• the non-aqueous ink composition was evaluated based on which of the "viscosity” and "volume-based cumulative 50% particle diameter (D50) of the pigment” had a larger rate of change (in the table, "storage stability”).
• Evaluation Criteria Evaluation 5 The rate of change in both the viscosity and the volume-based cumulative 50% particle size (D50) of the pigment is less than 3%.
• Evaluation 4 Either the change rate of the viscosity or the volume-based cumulative 50% particle diameter (D50) of the pigment is 3% or more and less than 5%.
• Evaluation 3 Either the change rate of the viscosity or the volume-based cumulative 50% particle diameter (D50) of the pigment is 5% or more and less than 8%.
• Evaluation 2 Either the change rate of the viscosity or the volume-based cumulative 50% particle diameter (D50) of the pigment is 8% or more and less than 10%.
• Evaluation 1 Either the change rate of the viscosity or the volume-based cumulative 50% particle diameter (D50) of the pigment is 10% or more.
• Ejection stability was evaluated for the non-aqueous ink compositions of Examples, Comparative Examples, and Reference Examples. Specifically, an inkjet printer (trade name: VersaArt RE-640, manufactured by Roland DG Co., Ltd.) is filled with a non-aqueous ink composition, and a recording medium (polyvinyl chloride film with glue (IMAGin JT5829R: MACtac Co., Ltd.) is used. )) in a bi-directional high-speed printing mode (360 x 720 dpi), solid and fine lines are printed by continuous printing at a substrate surface temperature of 40 ° C, and the presence or absence of missing dots, flight deflection, and ink splattering is visually observed.
• a recording medium polyvinyl chloride film with glue (IMAGin JT5829R: MACtac Co., Ltd.)
• a bi-directional high-speed printing mode 360 x 720 dpi
• Evaluation 3 ⁇ E is less than 3.0 and 2.5 or more.
• the non-aqueous ink compositions of Examples, Comparative Examples and Reference Examples were evaluated for surface drying properties. Specifically, the non-aqueous ink compositions of Examples and Comparative Examples were applied to a recording medium (adhesive polychlorinated A solid image was printed on a vinyl film (IMAGin JT5829R: manufactured by MACtac) in a high-quality print mode (1440 x 720 dpi), and the time taken to dry at 40°C was measured (referred to as "surface dryness" in the table). . Rating Criteria Rating 5: Dries in less than 2 minutes. Evaluation 4: Dry in 2 minutes or more and less than 4 minutes. Evaluation 3: Dry in 4 minutes or more and less than 6 minutes. Evaluation 2: Dry in 6 minutes or more and less than 8 minutes. Evaluation 1: It dries in 8 minutes or more.
• Evaluation Criteria Evaluation 5 No bleeding of ink was observed with a loupe. Evaluation 4: No bleeding of the ink was visually observed, and 6 pt characters were clear. Evaluation 3: Slight bleeding of the ink was visually observed, but the design was not damaged. Evaluation 2: Bleeding of the ink was visually observed, but the 6pt characters were recognizable. Evaluation 1: Remarkable bleeding of the ink was visually observed, and 6 pt characters were not visually recognized.
• the weather resistance of prints produced using the non-aqueous ink compositions of Examples, Comparative Examples and Reference Examples was evaluated.
• the non-aqueous ink compositions of Examples and Comparative Examples were applied to a recording medium (polyvinyl chloride film with glue (IMAGin JT5829R (manufactured by MACtac)) was printed with a solid image in a high-quality print mode (1440 ⁇ 720 dpi) and dried at 40° C. for 1 hour.
• the recorded matter thus obtained was put into a xenon weather meter (ATLAS Ci4000: manufactured by Toyo Seiki Co., Ltd.) and subjected to a cycle test.
• Test conditions are based on JIS K-5600-7-7, black panel temperature: 63°C, xenon lamp irradiance: 60W/m 2 , temperature inside test layer: 38°C, and humidity in segment 1 is 50%. 102 minutes in a state of maintaining at 200° C., and 18 minutes of water irradiation in segment 2, which was regarded as one cycle. With 50 cycles as one set, this cycle test was continued for 10 sets. The value of hue change ⁇ E before and after the test was evaluated, and the hue was evaluated under the following conditions.
• Evaluation 4 ⁇ E is less than 10.0 and 5.0 or more.
• Evaluation 3 ⁇ E is less than 15.0 and 10.0 or more.
• Evaluation 2 ⁇ E is less than 20.0 and 15.0 or more.
• Pigment Green 7 in the table is chlorinated copper phthalocyanine and corresponds to a halogenated phthalocyanine pigment (density: 2.0 g/cm 3 ).
• Pigment Green 36 in the table is a brominated chlorinated copper phthalocyanine and corresponds to a halogenated phthalocyanine pigment (density: 2.7 g/cm 3 ).
• Pigment Green 58 in the table is a halogenated zinc phthalocyanine and corresponds to a halogenated phthalocyanine pigment.
• C.I. I. Pigment Blue 15:4" (density: 1.6 g/cm 3 ) and "C.I. Pigment Yellow 155" (density: 1.45 g/cm 3 ) correspond to pigments that are not halogenated phthalocyanine pigments.
• the halogenated phthalocyanine pigment A3 is contained, and the organic solvent is an organic solvent B (alkylamide solvent (b1), cyclic amide solvent (b2), and lactone solvent (b3)
• organic solvent B alkylamide solvent (b1), cyclic amide solvent (b2), and lactone solvent (b3)
• the non-aqueous ink compositions of the examples containing at least one selected from the group consisting of (1) have high storage stability, high color tone stability, and high recovery from cleaning, even if they contain a halogenated phthalocyanine pigment. I understand.
• the content of the organic solvent B (alkylamide solvent) was 5% by mass or more.
• the non-aqueous ink compositions of Examples 3-9 to 3-14 had better color tone stability than that of Example 3-8.
• the storage stability and color tone stability were good.
• Examples 3-28 to 3-33 in which the volume-based cumulative 50% particle diameter (D50) and the volume-based cumulative 90% particle diameter (D90) of the halogenated phthalocyanine pigment A3 were changed, D50 is 150 nm or less and D90 is 300 nm or less, Examples 3-28 to 3-31 have better storage stability and color tone stability than the non-aqueous ink composition of Example 3-33.
• the content of the pigment A3 was 0.1% by mass or more and 8.0% by mass or less.
• the non-aqueous ink compositions of Examples 3-36 to 3-36 had better storage stability and color tone stability than the non-aqueous ink composition of Example 3-37.
• the resin having an intrinsic viscosity of 90 mL/g or more at 25°C in which the content of the resin having an intrinsic viscosity of 90 mL/g or more at 25°C was changed, the resin having an intrinsic viscosity of 90 mL/g or more at 25°C
• the non-aqueous ink compositions of Examples in the range of 5% by mass or less based on the total amount of the resin exhibited solid filling and ejection stability compared to the non-aqueous ink compositions of Examples in the range of more than 5% by mass. was improving.
• Example 3-55 to 3-60 and 3-66 in which the type of pigment dispersant was changed, Examples 3-56 to 3-60 and 3-66 in which a pigment dispersant having a basic group was used
• the non-aqueous ink composition of Example 3-55 had improved storage stability and ejection stability compared to the non-aqueous ink composition of Example 3-55.
• the non-aqueous ink compositions of Examples 3-57 to 3-60 and 3-66 which have an amine value in the range of 20 mgKOH/g or more and 100 mgKOH/g or less, have particularly improved storage stability and ejection stability. rice field.
• Example 3-61 to 3-64 in which the content of the pigment dispersant was changed, the range of 5 parts by mass to 150 parts by mass with respect to 100 parts by mass of the pigment in the non-aqueous ink composition
• the ink compositions of Examples 3-61 to 3-63 had improved surface drying properties compared to the ink composition of Example 3-64.
• Example 3-68 which did not contain a surfactant having a siloxane skeleton, had a relatively slightly reduced bleeding property.
• Comparative Examples 3-1 to 3-3 containing no organic solvent B (at least one selected from the group consisting of an alkylamide solvent (b1), a cyclic amide solvent (b2), and a lactone solvent (b3))
• the non-aqueous ink composition of -3 does not exhibit the effects of the present invention.
• non-aqueous ink composition of Reference Example 3-1 which did not contain the halogenated phthalocyanine pigment A3, had good storage stability and color tone stability even though it did not contain the organic solvent B.

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