Non-aqueous ink composition, ink set, recording method using the same, method for manufacturing a recording, recording, and inkjet recording apparatus

Abstract

The present invention provides a nonaqueous ink composition which is suitable for use as a nonaqueous ink composition to be ejected by means of an inkjet method even though at least one pigment that is selected from the group consisting of a perinone pigment, a diketopyrrolopyrrole pigment and a halogenated phthalocyanine pigment is contained therein.　A nonaqueous ink composition to be ejected by means of an inkjet method, the nonaqueous ink composition containing a pigment, a pigment dispersant and an organic solvent, wherein: the pigment contains at least one of a pigment A1 represented by formula (1-1), a pigment A2 represented by formula (1-2) and a halogenated phthalocyanine pigment A3; and the pH values of the pigment A1 and the pigment A2 are within the range of 3 to 9. (In formula (1-1), each of X1 to X12 independently represents a hydrogen atom, a halogen atom, an optionally branched alkyl group having 1 to 5 carbon atoms, an aromatic hydrocarbon group which may be substituted by a hydrogen atom, a cyano group, a nitro group, an amino group, -OH, -COOH, -COO-M+, -SO3H, -SO3 -M+, a phthalimide group which may be substituted by a hydrogen atom, a phthalimide methyl group, or a heterocyclic compound; and M+ represents a cation.) (In formula (1-2), each of X1 to X10 independently represents a hydrogen atom, a halogen atom, an optionally branched alkyl group having 1 to 5 carbon atoms, an aromatic hydrocarbon group which may be substituted by a hydrogen atom, a cyano group, a nitro group, an amino group, -OH, -COOH, -COO-M+, -SO3H, -SO3 -M+, a phthalimide group which may be substituted by a hydrogen atom, a phthalimide methyl group, or a heterocyclic compound; and M+ represents a cation.)

Description

[Technical Field]

[0001] The present invention relates to a non-aqueous ink composition, an ink set, a recording method using the same, a method for manufacturing a recording, a recording, and an inkjet recording apparatus. [Background technology]

[0002] As ink compositions, aqueous ink compositions, in which a colorant is dissolved or dispersed in water or a mixture of water and an organic solvent, and non-aqueous ink compositions, in which a colorant is dissolved or dispersed in an organic solvent that does not contain water, are widely used.

[0003] For example, 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. According to Patent Document 1, this non-aqueous ink composition has good storage stability because it contains a perinone-based pigment and an azo compound.

[0004] Furthermore, Patent Document 2 discloses a non-aqueous ink composition 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 the metal element. According to Patent Document 1, this non-aqueous ink composition is described as having excellent color saturation and excellent storage stability in the resulting recorded material.

[0005] Furthermore, Patent Document 3 discloses an inkjet recording ink composition comprising a copper complex dye (copper phthalocyanine), wherein the free copper ion concentration in the ink composition is 10 ppm or less. According to Patent Document 1, this ink composition is free of precipitates and exhibits high levels of various properties required for inkjet recording ink compositions. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2012-172070 [Patent Document 2] Japanese Patent Publication No. 2017-132891 [Patent Document 3] Japanese Patent Publication No. 2000-355665 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] Since perinone pigments are weather-resistant, ink compositions containing perinone pigments are particularly suitable for manufacturing records used outdoors.

[0008] However, our research has revealed that perinone-based pigments tend to aggregate in non-aqueous ink compositions. This can lead to clogging of the nozzles that eject ink in inkjet printers, resulting in problems such as reduced inkjet ejection performance, and other issues that prevent the composition from meeting the required characteristics of a non-aqueous ink ejected by an inkjet method.

[0009] Furthermore, when ejecting ink by the inkjet method, solid components such as resins contained in the non-aqueous ink composition may clog the nozzles in the inkjet head when the ink composition is ejected through the inkjet head.

[0010] Therefore, inkjet recording devices are equipped with a cleaning and recovery function to resolve nozzle clogging in the inkjet head.

[0011] However, our research has revealed that even when a non-aqueous ink composition containing diketopyrrolopyrrole pigment is ejected by an inkjet method, and then an attempt is made to clear nozzle clogging in the inkjet head using a cleaning recovery function, the nozzle clogging cannot be sufficiently cleared. In this specification, the ability to clear nozzle clogging in the inkjet head using a cleaning recovery function is referred to as cleaning recovery performance.

[0012] Furthermore, halogenated phthalocyanine pigments are known in which some of the hydrogen atoms in a phthalocyanine structure are replaced with halogens. When phthalocyanine pigments are halogenated, they become pigments that exhibit a green color. By using a green ink containing a green pigment in addition to the usual four color inks, the saturation is improved compared to reproducing green with only two colors, yellow and cyan, thus improving color reproduction. In addition, phthalocyanine pigments generally have higher weather resistance than yellow pigments used in yellow inks. Therefore, by using a green ink containing halogenated phthalocyanine pigments, the weather resistance of the resulting recording can also be improved compared to using only two colors, yellow and cyan.

[0013] However, our research has revealed that non-aqueous ink compositions containing halogenated phthalocyanine pigments have a problem in that the pigment tends to precipitate in the non-aqueous ink composition, resulting in poor storage stability. Furthermore, with such non-aqueous ink compositions that have poor storage stability, even if the cleaning and recovery function of the inkjet recording device is used to clear nozzle clogging in the inkjet head, the nozzle clogging may not be sufficiently cleared.

[0014] Furthermore, our research has revealed that when a non-aqueous ink composition containing halogenated phthalocyanine pigment is left standing for a long period of time, the pigment precipitates, causing a change in color tone and reducing color stability.

[0015] The present invention aims to provide a non-aqueous ink composition that can be suitably used as a non-aqueous ink composition ejected by an inkjet method, even if it contains a perinone-based pigment.

[0016] Furthermore, the present invention aims to provide a non-aqueous ink composition that has high storage stability and high cleaning recovery even when containing a diketopyrrolopyrrole pigment.

[0017] Furthermore, the present invention aims to provide a non-aqueous ink composition that contains a halogenated phthalocyanine pigment and exhibits high storage stability, color stability, and cleaning recovery. [Means for solving the problem]

[0018] The inventors of the present invention conducted diligent research to solve the above problems and found that a non-aqueous ink composition containing a perinone-based pigment within a predetermined pH range can solve the above problems, thus completing the present invention.

[0019] Furthermore, the present inventors conducted diligent studies to solve the above problems and found that a non-aqueous ink composition containing a diketopyrrolopyrrole pigment within a predetermined pH range can solve the above problems, thus completing the present invention.

[0020] Furthermore, the inventors diligently studied to solve the above problems and found that a non-aqueous ink composition containing a halogenated phthalocyanine pigment and a predetermined organic solvent can solve the above problems, thus completing the present invention. Specifically, the present invention provides the following.

[0021] (1) A non-aqueous ink composition that is ejected by an inkjet method and contains a pigment, a pigment dispersant, and an organic solvent, The aforementioned pigment contains at least one of pigment A1 represented by the following formula (1-1) or pigment A2 represented by the following formula (1-2). The pH of pigments A1 and A2 is within the range of 3 to 9. Non-aqueous ink composition. [ka] (In formula (1-1), X1 to X12 are each independently hydrogen, a halogen atom, an optionally branched alkyl group having 1 to 5 carbon atoms, an aromatic hydrocarbon group optionally substituted with a hydrogen atom, a cyano group, a nitro group, an amino group, -OH, -COOH, -COO , - , , , - , , + , , , + , , ,

[0023] , + , , + , + , , , - ,

[0022] ,

[0025] , , , ,

[0024] M + , -SO3H, -SO3 - M + , an optionally substituted phthalimide group, a phthalimidomethyl group, or a heterocyclic compound, and M + represents a cation.)

Chemical formula

[0022] (2) The non-aqueous ink composition according to (1), wherein the volume-based cumulative 90% particle diameter (D90) of the pigments A1 and A2 is 500 nm or less.

[0023] (3) The non-aqueous ink composition according to (1) or (2), wherein the content of the pigments A1 and A2 is 0.1% by mass or more and 8.0% by mass or less in the total amount of the non-aqueous ink composition.

[0024] (4) The non-aqueous ink composition according to any one of (1) to (3), wherein the organic solvent contains the following organic solvent B. Organic solvent B: at least one selected from the group consisting of an alkylamide-based solvent (b1), a cyclic amide-based solvent (b2), and a lactone-based solvent (b3)

[0025] (5) A non-aqueous ink composition dispensed by an inkjet method, comprising a pigment, a pigment dispersant, and an organic solvent, wherein the pigment contains 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).

[0026] (6) The non-aqueous ink composition according to (5), wherein the volume-based cumulative 50% particle size (D50) of pigment A3 is 30 nm or more and 150 nm or less.

[0027] (7) The non-aqueous ink composition according to (5) or (6), wherein the volume-based cumulative 90% particle size (D90) of the pigment A3 is 50 nm or more and 300 nm or less.

[0028] (8) The non-aqueous ink composition according to any one of (5) to (7), wherein the content of pigment A3 is 0.1% by mass or more and 8.0% by mass or less in the total amount of the non-aqueous ink composition.

[0029] (9) The non-aqueous ink composition according to any one of (5) to (8), wherein the pigment A3 is at least one selected from the group consisting of chlorinated phthalocyanine pigment, brominated phthalocyanine pigment, and chlor-brominated phthalocyanine pigment.

[0030] (10) The non-aqueous ink composition according to any one of (5) to (9), wherein the pigment A3 is at least one selected from the group consisting of copper halide phthalocyanine pigment and zinc halide phthalocyanine pigment.

[0031] (11) The non-aqueous ink composition according to any one of (5) to (10), wherein the organic solvent contains a glycol ether solvent.

[0032] (12) The non-aqueous ink composition according to any one of (5) to 11, wherein the water content is in the range of 1.0% by mass or less of the total amount of the non-aqueous ink composition.

[0033] (13) The non-aqueous ink composition according to any one of (4) to (12), wherein the organic solvent B contains an alkylamide solvent (b1).

[0034] (14) The alkylamide solvent (b1) is the non-aqueous ink composition described in (13) which is represented by the following general formula (2). [ka] (In formula (2), R1 is hydrogen or an alkyl group having 1 to 4 carbon atoms, and R2 and R3 each independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms.)

[0035] (15) The non-aqueous ink composition according to (14), wherein the alkylamide solvent (b1) contains at least one selected from the group consisting of N,N-diethylformamide, N,N-diethylpropanamide, and N,N-diethylacetamide.

[0036] (16) The non-aqueous ink composition according to any one of (4) to (12), wherein the organic solvent contains a cyclic amide solvent (b2).

[0037] (17) The cyclic amide solvent (b2) is the non-aqueous ink composition described in (16) and represented by the following general formula (3). [ka] (In formula (3), R4 is an alkylene group having 3 to 5 carbon atoms, and R5 represents hydrogen, an alkyl group having 1 to 4 carbon atoms, or an unsaturated hydrocarbon group.)

[0038] (18) The non-aqueous ink composition according to (17), wherein the cyclic amide solvent (b2) contains at least one selected from the group consisting of ε-caprolactam, N-methylcaprolactam, and N-vinylcaprolactam.

[0039] (19) The non-aqueous ink composition according to any one of (4) to (12), wherein the organic solvent contains a lactone-based solvent (b3).

[0040] (20) The lactone-based solvent (b3) is the non-aqueous ink composition described in (19) which is represented by the following general formula (4). [ka] (In formula (4), R6 is an alkylene group having 3 to 5 carbon atoms, and R7 represents hydrogen or an alkyl group having 1 to 2 carbon atoms.)

[0041] (21) The non-aqueous ink composition according to (20), wherein the lactone solvent (b3) contains at least one selected from the group consisting of γ-butyrolactone, γ-valerolactone, and ε-caprolactone.

[0042] (22) The non-aqueous ink composition according to any one of (4) to (21), wherein the content of the organic solvent B is in the range of 1% by mass or more and 90% by mass or less in the total amount of the non-aqueous ink composition.

[0043] (23) The non-aqueous ink composition according to any one of (1) to (22), wherein the pigment dispersant has a basic group.

[0044] (24) The non-aqueous ink composition according to any one of (1) to (23), wherein the amine value of the pigment dispersant is in the range of 20 mg KOH / g or more and 100 mg KOH / g or less.

[0045] (25) The non-aqueous ink composition according to any one of (1) to (24), wherein the content of the pigment dispersant is in the range of 5 parts by mass or more and 150 parts by mass or less per 100 parts by mass of pigment in the non-aqueous ink composition.

[0046] (26) A non-aqueous ink composition according to any one of (1) to (25), wherein the resin contains a resin having an intrinsic viscosity of 90 mL / g or more at 25°C, and the amount of the resin is within the range of 5% by mass or less of the total amount of resin.

[0047] (27) The non-aqueous ink composition according to (26), wherein the resin contains at least one selected from the group consisting of acrylic resins, vinyl chloride resins, cellulose resins, polyester resins, and polyurethane resins.

[0048] (28) The non-aqueous ink composition according to any one of (1) to (27), further comprising a surfactant, wherein the surfactant comprises a surfactant having a siloxane skeleton.

[0049] (29) A non-aqueous ink composition according to any one of (1) to (28) used in an inkjet recording device comprising a storage mechanism for storing a non-aqueous ink composition, an inkjet ejection port, and a tube for circulating the non-aqueous ink composition, wherein the tube is connected to the storage mechanism and the inkjet ejection port and comprises a valve mechanism for adjusting the flow path of the non-aqueous ink composition.

[0050] (30) Dispense the non-aqueous ink composition described in any of (1) to (29) onto the surface of the substrate using an inkjet method. Recording method.

[0051] A method for producing a recording, comprising ejecting a non-aqueous ink composition described in any of (1) to (29) onto the surface of a substrate using an inkjet method.

[0052] (32) An ink set comprising at least one of the non-aqueous ink compositions described in any of (1) to (29).

[0053] (33) A recording material having a printed layer of a non-aqueous ink composition according to any one of (1) to (29) formed on the surface of a substrate.

[0054] (34) An inkjet recording apparatus for ejecting a 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; an inkjet ejection port; and a tube for circulating the non-aqueous ink composition, wherein the tube is connected to the storage mechanism and the inkjet ejection port and comprises a valve mechanism for adjusting the flow path of the non-aqueous ink composition. [Effects of the Invention]

[0055] 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-based pigment is used as the pigment.

[0056] Furthermore, the non-aqueous ink composition of the present invention exhibits high storage stability and high cleaning recovery even when using a pigment containing diketopyrrolopyrrole pigment as the pigment.

[0057] Furthermore, the non-aqueous ink composition of the present invention exhibits high storage stability, color stability, and cleaning recovery even when containing halogenated phthalocyanine pigments. [Modes for carrying out the invention]

[0058] The following describes specific embodiments of the present invention in detail. However, the present invention is not limited in any way to the following embodiments, and can be implemented with appropriate modifications within the scope of the object of the present invention.

[0059] ≪1. Overview≫ The non-aqueous ink composition of one embodiment of the present invention (for example, the non-aqueous ink compositions of the first, second, and third embodiments) is a non-aqueous ink composition that is ejected by an inkjet method and contains a pigment, a pigment dispersant, and an organic solvent. Hereinafter, "non-aqueous ink composition" means an ink composition containing an organic solvent that is manufactured without intentionally containing water, unlike an aqueous ink composition which has water as its main component.

[0060] Furthermore, the ink compositions according to this embodiment (including the non-aqueous ink compositions of the first, second, and third embodiments described below) are preferably ink compositions that can obtain a record by the drying (volatilization) of the organic solvent. Specifically, in such ink compositions, the volatile components such as organic solvents contained in the ink composition dry (volatilize), and the residue accumulates on the surface of the substrate, forming a record. This ink composition is different from active energy ray curing type ink compositions that polymerize and harden on the substrate by irradiation with active energy rays such as ultraviolet rays. Active energy ray curing type ink compositions contain polymerizable compounds as essential components, but ink compositions that can obtain a record by the drying (volatilization) of the organic solvent contain an organic solvent, but do not require the inclusion of polymerizable compounds as an essential component; they may or may not contain polymerizable compounds.

[0061] Furthermore, the pigment contained in this non-aqueous ink composition is characterized by containing at least one of pigment A1 represented by the following formula (1-1) or pigment A2 represented by the following formula (1-2), and the pH of pigments A1 and A2 is in the range of 3 to 9.

[0062] [ka] (In formula (1-1), X1 to X12 are substituents containing hydrogen. X1 to X12 can each be independently hydrogen, a halogen atom, a branched alkyl group having 1 to 5 carbon atoms, an aromatic hydrocarbon group which may be substituted with a hydrogen atom, a cyano group, a nitro group, an amino group, -OH, -COOH, or -COO - M + -SO3H, -SO3 - M + , a phthalimide group, a phthalimidemethyl group, or a heterocyclic compound, which may have a hydrogen atom substituted, M + (This indicates a cation.) [ka] (In formula (1-2), X1 to X10 are independently hydrogen, halogen atom, branched alkyl group having 1 to 5 carbon atoms, aromatic hydrocarbon group which may be substituted with a hydrogen atom, cyano group, nitro group, amino group, -OH, -COOH, -COO) - M + -SO3H, -SO3 - M + , a phthalimide group, a phthalimidemethyl group, or a heterocyclic compound, which may have a hydrogen atom substituted, M + (This indicates a cation.)

[0063] Furthermore, one embodiment of the present invention is a non-aqueous ink composition that is ejected by an inkjet method and contains a pigment, a pigment dispersant, and an organic solvent. The pigment contained in this non-aqueous ink composition contains halogenated phthalocyanine pigment A3, and the organic solvent contains the following organic solvent B.

[0064] Organic solvent B: At least one selected from the group consisting of alkylamide solvents (b1), cyclic amide solvents (b2), and lactone solvents (b3).

[0065] The following describes specific embodiments of the present invention in detail. ≪1-1. Non-aqueous ink composition of the first embodiment≫ The non-aqueous ink composition of the first embodiment according to this embodiment is a non-aqueous ink composition that is ejected by an inkjet method and contains a pigment, a pigment dispersant, and an organic solvent. Here, "non-aqueous ink composition" means an ink composition containing an organic solvent that is manufactured without intentionally containing water, unlike an aqueous ink composition which has water as its main component.

[0066] Furthermore, the pigment contained in this non-aqueous ink composition is characterized by containing pigment A1 represented by the following formula (1-1), and the pH of pigment A1 is in the range of 3 to 9.

[0067] [ka] (In formula (1-1), X1 to X12 are substituents containing hydrogen. X1 to X12 can each be independently hydrogen, a halogen atom, a branched alkyl group having 1 to 5 carbon atoms, an aromatic hydrocarbon group which may be substituted with a hydrogen atom, a cyano group, a nitro group, an amino group, -OH, -COOH, or -COO - M + -SO3H, -SO3 - M + , a phthalimide group, a phthalimidemethyl group, or a heterocyclic compound, which may have a hydrogen atom substituted, M + (This indicates a cation.)

[0068] By including pigment A1, whose pH is controlled within the range of 3 to 9, aggregation of pigments can be suppressed in the non-aqueous ink composition. This allows the non-aqueous ink composition to meet various required properties when ejected by an inkjet method.

[0069] Pigment A1 with a pH of 3 to 9 can be obtained, for example, by treating the surface of the pigment by washing it with a solution (acidic solution, alkaline solution, or neutral solution), or by changing the types of substituents (X1 to X12) in the benzene ring of the structure of formula (1-1), or by applying both of these treatments.

[0070] Methods for changing the types of substituents (X1 to X12) in a benzene ring include dispersing the pigment in an organic solvent and introducing the desired substituents using an additive capable of introducing specific substituents. For example, the pH of the pigment can also be adjusted by the method described in Japanese Patent No. 2993392.

[0071] Furthermore, when changing the types of substituents (X1 to X12) in the benzene ring, the substitution position of substituents X1 to X12 is not particularly limited, as long as the pH of pigment A1 is within the range of 3 to 9, and any of the 12 substitution positions on the benzene ring is acceptable. The number of substituents is also not particularly limited.

[0072] In this specification, the pH of pigment A1 is the pH measured according to the test method of JIS K5101-17-1:2004. The same method is used to measure the pH of pigment A2, as described later.

[0073] 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, and more preferably 5 or higher. In particular, when the pH of pigment A1 is 9 or lower, the pigment dispersant adheres more easily, making it possible to more effectively suppress the aggregation of pigment A1 in the non-aqueous ink composition. This improves the discharge stability and color stability of the non-aqueous ink composition.

[0074] In the non-aqueous ink composition according to this embodiment, the water content is preferably 5.0% by mass or less, preferably 1.0% by mass or less, and more preferably 0.5% by mass or less of the total amount of the non-aqueous ink composition. Because pigment A1 is highly hydrophobic, non-aqueous inkjet compositions containing this pigment tend to deteriorate relatively easily upon contact with water, leading to poor storage stability. By reducing the water content in the non-aqueous ink composition to contain as little water as possible (intentionally omitting water), it is possible to improve storage stability, cleaning recovery, etc. The same applies to the non-aqueous ink compositions of the second and third embodiments described later.

[0075] The average particle size of 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. This makes it possible to more effectively suppress the aggregation of pigment A1 in the non-aqueous ink composition, and makes it more suitable for use as a non-aqueous ink composition ejected by an inkjet method. The lower limit of the volume-based cumulative 90% particle size (D90) is preferably 50 nm or more, and preferably 100 nm or more. Having the volume-based cumulative 90% particle size (D90) of pigment A1 within this range improves the storage stability of the non-aqueous ink composition. The same applies to the preferred average particle size of pigment A2 in the non-aqueous ink composition of the second embodiment described later.

[0076] In this specification, "volume-based cumulative 50% particle diameter (D50)" refers to the particle diameter at which the cumulative volume calculated from the smallest diameter side reaches 50%. "Volume-based cumulative 50% particle diameter (D50)" may also be referred to as "volume-average particle diameter D50" or "median diameter." "Volume-based cumulative 90% particle diameter (D90)" refers to the particle diameter at which the cumulative volume calculated from the smallest diameter side reaches 90%. "Volume-based cumulative 50% particle diameter (D50)" and "volume-based cumulative 90% particle diameter (D90)" can be measured using a particle size distribution analyzer (NANOTRACWAVE particle size analyzer manufactured by Microtrac Bell Co., Ltd.). The same applies to the non-aqueous ink compositions of the second and third embodiments described later.

[0077] The content of pigment A1 is not particularly limited, but the lower limit of the pigment A1 content is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more, of the total amount of the non-aqueous ink composition. A pigment A1 content of 0.1% by mass or more of the total amount of the non-aqueous ink composition makes it possible to improve print density and increase the color reproduction range of the recorded material obtained by combining it with other colored non-aqueous ink compositions. Furthermore, the upper limit of the pigment A1 content 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. A pigment A1 content of 8.0% by mass or less of the total amount of the non-aqueous ink composition makes it possible to relatively increase the content of other additives, and furthermore, it suppresses the increase in viscosity caused by increasing the pigment A1 content, thus suppressing nozzle clogging of the inkjet head.

[0078] Examples of pigment A1 represented by formula (1-1) include CI Pigment Orange 43. Pigment A1 represented by formula (1-1) may be synthesized, for example, by treating the surface of commercially available CI Pigment Orange 43 by washing it with a solution (acidic solution, alkaline solution, or neutral solution), or by changing the types of substituents (X1 to X12) in the benzene ring in the structure of formula (1-1), or by performing both treatments. Examples of commercially available products include A-76 from Arimoto Chemical Co., Ltd., Hostaperm Orange GR and PV Gast Orange GRL from Clariant, Inc., Fasogen Super Orange 6200 from DIC Corporation, and Lionogen Orange GR-F from Toyo Ink Co., Ltd.

[0079] Furthermore, the non-aqueous ink composition according to this embodiment may further contain colorants (including pigments and dyes) other than the pigment A1 described above. Examples of such colorants include pigments and dyes with hues similar to pigment A1 (for example, orange, magenta, yellow, and red).

[0080] Examples of organic pigments other than the aforementioned pigment A1, using their Color Index (CI) numbers, are: CI 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; CI Pigment Red 5, 7, 9, 12, 48, 49, 52, 53 Examples include 57:1, 97, 112, 122, 123, 146, 149, 150, 168, 177, 180, 184, 192, 202, 206, 208, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 238, 240, 254, 255, 269, 291, CI Pigment Orange 16, 36, 43, 51, 55, 59, 61, 64, 71, 73, CI Pigment Violet 19, 23, 29, 30, 37, 40, 50, CI Pigment Brown 23, 25, 26, etc.

[0081] Furthermore, a dispersion aid (pigment derivative), described later, may be used in conjunction with the pigment dispersant. This can improve the dispersion stability of the pigment.

[0082] Next, we will describe each component contained in the non-aqueous ink composition according to this embodiment.

[0083] [Organic solvents] The 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 from the viewpoint of dispersing the pigment containing pigment A1 and more effectively achieving the effects of the present invention, it is preferable that it contains organic solvent B (at least one selected from the group consisting of alkylamide solvents (b1), cyclic amide solvents (b2), and lactone solvents (b3)).

[0084] The alkylamide solvent (b1), cyclic amide solvent (b2), and lactone solvent (b3) contained in organic solvent B will be described below.

[0085] (1) Alkylamide solvents Alkylamide solvents are solvents containing alkyl groups (C n H 2n+1 A solvent comprising a compound having a -) and a -C(=O)-N- group (amide bond), and composed of a compound consisting of hydrogen or an alkyl group and a -C(=O)-N- group. For example, alkylamide solvents having the following structures are preferably used.

[0086] [ka] (In formula (2), R1 is hydrogen or an alkyl group having 1 to 4 carbon atoms, and R2 and R3 each independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms.)

[0087] In formula (2), R2 and R3 are preferably alkyl groups having 1 to 4 carbon atoms, and more preferably alkyl groups having 2 to 4 carbon atoms.

[0088] Examples of alkylamide solvents include N,N-diethylformamide, N,N-diethylacetamide, N,N-dipropylformamide, N,N-dibutylformamide, N,N-diethylpropanamide, N,N-dipropylpropanamide, N-ethylformamide, and N-ethylacetamide. Among these, from the viewpoint of particularly achieving the effects of the present invention, it is preferable to contain at least one selected from the group consisting of N,N-diethylformamide, N,N-diethylpropanamide, and N,N-diethylacetamide.

[0089] The content of alkylamide solvent (b1) is not particularly limited, but the lower limit of the content of alkylamide solvent (b1) is preferably in the range of 1% by mass or more, more preferably in the range of 5% by mass or more, and even more preferably in the range of 8% by mass or more, based on the total amount of the non-aqueous ink composition.

[0090] The upper limit of the alkylamide solvent (b1) content is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 75% by mass or less, based on the total amount of the non-aqueous ink composition.

[0091] (2) Cyclic amide solvents A cyclic amide solvent (b2) is a solvent having a cyclic structure and a -C(=O)-N- group in that cyclic structure. For example, cyclic amide solvents having the following structures can be preferably used.

[0092] [ka] (In formula (3), R4 is an alkylene group having 3 to 5 carbon atoms, and R5 represents hydrogen, an alkyl group having 1 to 4 carbon atoms, or an unsaturated hydrocarbon group.)

[0093] Examples of cyclic amide solvents (b2) include N-methylcaprolactam, N-acetylcaprolactam, ε-caprolactam, N-vinylcaprolactam, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-ethyl-ε-caprolactam, N-propyl-ε-caprolactam, and N-methyl-ε-caprolactam. Among these, it is preferable to contain at least one selected from the group consisting of ε-caprolactam, N-methylcaprolactam, and N-vinylcaprolactam.

[0094] The content of the cyclic amide solvent (b2) is not particularly limited, but the lower limit of the content of the cyclic amide solvent (b2) is preferably in the range of 1% by mass or more, more preferably in the range of 5% by mass or more, and even more preferably in the range of 8% by mass or more, based on the total amount of the non-aqueous ink composition.

[0095] 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 even more preferably 75% by mass or less, based on the total amount of the non-aqueous ink composition.

[0096] (3) Lactone-based solvents Lactone-based solvents are solvents having a cyclic ester structure. For example, lactone-based solvents having the following structures are preferably used.

[0097] [ka] (In formula (4), R6 is an alkylene group having 3 to 5 carbon atoms, and R7 represents hydrogen or an alkyl group having 1 to 2 carbon atoms.) More preferably, R6 is an alkylene group having 4 to 5 carbon atoms, and more preferably an alkylene group having 5 carbon atoms.

[0098] Examples of lactone-based solvents (b3) include γ-butyrolactone, δ-valerolactone, δ-hexanolactone, ε-caprolactone, γ-valerolactone, γ-hexalactone, γ-heptalactone, γ-octaractone, γ-nonalactone, γ-decalactone, γ-undecalactone, δ-heptalactone, δ-octaractone, δ-nonalactone, δ-decalactone, and δ-undecalactone. Among these, γ-butyrolactone, δ-valerolactone, δ-hexanolactone, ε-caprolactone, and γ-valerolactone are more preferred, with ε-caprolactone being even more preferred.

[0099] The content of the lactone-based solvent (b3) is not particularly limited, but the lower limit of the lactone-based solvent (b3) content is preferably in the range of 1% by mass or more, more preferably in the range of 5% by mass or more, and even more preferably in the range of 8% by mass or more, based on the total amount of the non-aqueous ink composition.

[0100] The upper limit of the lactone-based solvent (b3) content is preferably 90% by mass or less, more preferably 70% by mass or less, and even more preferably 50% by mass or less, based on the total amount of the non-aqueous ink composition.

[0101] Among organic solvents B, it is preferable that they contain either an alkylamide solvent (b1) or a cyclic amide solvent (b2), with the alkylamide solvent (b1) being more preferable. This makes it possible to more effectively disperse the pigment containing pigment A1, thereby improving the storage stability and cleaning recovery of the non-aqueous ink composition. Furthermore, it results in a non-aqueous ink composition with high surface drying properties on the substrate, reducing print bleeding and resulting in clearer printing.

[0102] Organic solvent B is sufficiently effective when it contains at least one of alkylamide solvents (b1), cyclic amide solvents (b2), or lactone solvents (b3), but two or more types of solvents may be mixed from among organic solvent B. By mixing two or more types, a desired balance of storage stability, material suitability, surface drying properties, and cleaning recovery properties can be achieved. When mixing two or more types, the lower limit of the total content of organic solvent B is preferably in the range of 1% by mass or more, more preferably in the range of 5% by mass or more, and even more preferably in the range of 10% by mass or more, of the total amount of the non-aqueous ink composition. The upper limit of the total content of organic solvent B is preferably 90% by mass or less of the total amount of the non-aqueous ink composition.

[0103] [Other organic solvents] The non-aqueous ink composition according to this embodiment may contain organic solvents other than the organic solvent B described above. Specifically, examples include glycol ether dialkyls in which the OH groups at both ends of the glycol are alkyl-substituted, glycol ether monoalkyls in which one of the OH groups of the glycol is alkyl-substituted, and carbonate esters.

[0104] Glycol ether solvents include glycol ether dialkyls, in which the OH groups at both ends of the glycol are alkyl-substituted, and glycol ether monoalkyls, in which one of the OH groups of the glycol is alkyl-substituted. Examples of glycol ether solvents include those containing at least one glycol ether dialkyl and glycol ether monoalkyl represented by the following formula (5).

[0105] R8-(-O-R9) n -OR 10 ...(5) (In formula (5), R8, R 10 Each of these independently represents either hydrogen or a branched alkyl group having 1 to 8 carbon atoms, and R9 represents a branched alkylene group having 1 to 4 carbon atoms. n represents an integer between 1 and 6.

[0106] Examples of such glycol ether solvents 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, and propylene glycol mono-n-butyl ether. Alkylene glycol monoalkyl ethers such as propylene glycol mono-isobutyl ether, propylene glycol mono-t-butyl ether, propylene glycol mono-2-ethylhexyl ether, dipropylene glycol monomethyl (or ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl) ether, tripropylene glycol monomethyl (or ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl) ether, tetrapropylene glycol monomethyl ether (or ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl);Ethylene glycol dibutyl ether, ethylene glycol dipropyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl 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, tetraethylene glycol diethyl ether, tetraethylene glycol Examples of polyhydric alcohol dialkyl ethers include tripropyl methyl 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, dipropylene glycol methyl butyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, and tripropylene glycol ethyl methyl ether.

[0107] Among these, 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, and tripropylene glycol ethyl methyl ether are among the preferred candidates.

[0108] Furthermore, it is preferable to combine two or more glycol ether solvents with different flash points. By including a glycol ether solvent with a high flash point (for example, a flash point of 70°C or higher), a non-aqueous ink composition with high cleaning recovery properties can be obtained. By including 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 properties on the substrate can be obtained. By including a glycol ether solvent with a flash point of 70°C or higher and a glycol ether solvent with a flash point of less than 70°C, it becomes possible to achieve both high cleaning recovery properties and surface drying properties on the substrate, resulting in a non-aqueous ink composition that particularly effectively demonstrates the effects of the present invention.

[0109] Furthermore, other solvents other than glycol ether solvents may be included. Specifically, these include carbonate esters such as propylene carbonate and ethylene carbonate, oxazolidinone solvents such as 3-methyl-2-oxazolidinone, 3-ethyl-2-oxazolidinone, and N-vinylmethyloxazolidinone, acetate solvents such as triethylene glycol butyl ether acetate, ethylene 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, and 1-methoxy-2-propyl acetate, as well as 3-methoxypropanamide, 3-butoxypropanamide, N,N-dimethyl-3-methoxypropanamide, N,N-dibutyl-3-methoxypropanamide, and N,N-dibutyl-3 -Alkylamide solvents (b1) such as butoxypropanamide and N,N-dimethyl-3-butoxypropanamide, and cyclic amide solvents (b2) other than amide solvents, as well as alkyl alcohols with 1 to 5 carbon atoms such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, and n-pentanol; monohydric alcohol solvents such as 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-propanol, 1-methoxy-2-propanol, and 3-methoxy-n-butanol, as well as ketones or keto alcohols such as acetone and diacetone alcohol; ethers such as tetrahydrofuran and dioxane; oxyethylene or oxypropylene copolymers such as polyethylene glycol and polypropylene glycol;Ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-propanediol, isobutylene glycol, triethylene glycol, tripropylene glycol, tetraethylene glycol, 1,3-propanediol, 2-methyl-1,2-propanediol, 2-methyl-1,2-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,3- Examples include diols such as butanediol, 3-methyl-1,5-pentanediol, and 2-methyl-2,4-pentanediol; triols such as glycerin, trimethylolethane, trimethylolpropane, and 1,2,6-hexanetriol; tetrahydric alcohols such as mesoerythritol and pentaerythritol; and alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-ethylethanolamine, N-butylethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, and N-butyldiethanolamine. It is preferable to select a solvent with an appropriate HLB value depending on the resin and dispersant being combined.

[0110] The content of other organic solvents is not particularly limited, but the lower limit of the content of other organic solvents is preferably in the range of 10% by mass or more, more preferably in the range of 20% by mass or more, and even more preferably in the range of 30% by mass or more. The upper limit of the content of other organic solvents is preferably in the range of 85% by mass or less, more preferably in the range of 80% by mass or less, and even more preferably in the range of 75% by mass or less.

[0111] [Pigment dispersant] In the non-aqueous ink composition according to this embodiment, a dispersant may be used as needed. Any dispersant used in non-aqueous ink compositions can be used as the dispersant. A polymeric dispersant is preferable as the dispersant. Such dispersants have a main chain made of polyester, polyacrylic, polyurethane, polyamine, polycaprolactone, etc., and side chains that have polar groups such as amino groups, carboxyl groups, sulfone groups, and hydroxyl groups. Examples of polyacrylic dispersants include 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 Bic Chemie), EfkaPX4310, PX4320, PX4330, PA4401, 4402, PA4403, 4570, 7411, 7477, PX4700, PX4701 (manufactured by BASF), and TREPLUS. Products such as D-1200, D-1410, D-1420, MD-1000 (manufactured by Otsuka Chemical Co., Ltd.), Floren DOPA-15BHFS, 17HF, 22, G-700, 900, NC-500, and GW-1500 (manufactured by Kyoeisha Chemical Co., Ltd.) are used. Examples of polycaprolactone-based dispersants include Ajisper PB821, PB822, PB881 (manufactured by Ajinomoto Fine Techno Co., Ltd.), Hinoact KF-1000, T-6000, T-7000, T-8000, T-8000E, T-9050 (manufactured by Kawaken Fine Chemical Co., Ltd.), Solsperse 20000, 24000, 32000, 32500, 32550, 32600, 33000, 33500, 34000, 35200, 36000, 37500, 39000, 71000, 76400, 76500, 86000, 88000, J180, J200 (manufactured by Lubrizol), and TEGO. Dispers 652, 655, 685, 688, and 690 (manufactured by Evonik Japan) are used.Preferred dispersants include BYKJET-9130, 9131, 9132, 9133, 9151, EfkaPX4310, PX4320, PX4330, PX4700, PX4701, Solsperse20000, 24000, 32000, 33000, 33500, 34000, 35200, 39000, 71000, 76500, 86000, 88000, J180, J200, TEGO Dispers655, 685, 688, 690, etc. These can be used individually or in mixtures thereof.

[0112] In particular, in the non-aqueous ink composition according to this embodiment containing pigment A1 with 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, using a pigment dispersant having a basic group can more effectively suppress the aggregation of pigment A1 in the non-aqueous ink composition. The same applies to the non-aqueous ink composition containing pigment A2 with a pH of 3 or more and 9 or less, which will be described later.

[0113] In particular, when the pH of pigment A1 is 8 or lower, the pigment dispersant having a basic group adheres more easily to the surface of pigment A1, making it possible to more effectively suppress the aggregation of pigment A1 in the non-aqueous ink composition.

[0114] Among these, it is preferable to use a pigment dispersant with an amine value in the range of 20 mg KOH / g to 100 mg KOH / g. This can further effectively suppress the aggregation of pigment A1 in the non-aqueous ink composition. In particular, when the pH of pigment A1 is 8 or less, the pigment dispersant with an amine value in the predetermined range adheres more easily to the surface of pigment A1, making it possible to further effectively suppress the aggregation of pigment A1 in the non-aqueous ink composition. The same applies to non-aqueous ink compositions containing pigment A2 with a pH of 3 to 9, which will be described later.

[0115] The content of the pigment dispersant is not particularly limited, but the lower limit of the pigment dispersant content is preferably 5 parts by mass or more, more preferably 15 parts by mass or more, and even more preferably 20 parts by mass or more, per 100 parts by mass of pigment in the non-aqueous ink composition. The upper limit of the pigment dispersant content is preferably 150 parts by mass or less, more preferably 125 parts by mass or less, and even more preferably 100 parts by mass or less, per 100 parts by mass of pigment in the non-aqueous ink composition.

[0116] [Dispersing agent] In the non-aqueous ink composition according to this embodiment, a dispersion aid may be used as needed. The dispersion aid is adsorbed onto the surface of the colorant (pigment), and its functional group enhances the affinity of the organic solvent and dispersant in the non-aqueous ink composition, thereby improving dispersion stability. As the dispersion aid, derivatives of the pigments described above are preferred, and known pigment derivatives having functional groups such as acidic groups, basic groups, and neutral groups in the organic pigment residues can be used. The same applies to the non-aqueous ink compositions of the second and third embodiments described later.

[0117] [resin] The non-aqueous ink composition according to this embodiment does not necessarily contain a resin, but it may contain one. By including a resin, the fixation, water resistance, and stretchability of the recording layer formed by the non-aqueous ink composition can be improved. Furthermore, the glossiness of the resulting recording can be improved. The same applies to the non-aqueous ink compositions of the second and third embodiments described later.

[0118] The resin is not particularly limited, but examples include acrylic resins, polystyrene resins, polyester resins, vinyl chloride resins, vinyl acetate resins, vinyl chloride vinyl acetate copolymer resins, polyethylene resins, polyurethane resins, rosin-modified resins, phenolic resins, terpene resins, polyamide resins, vinyltoluene-α-methylstyrene copolymers, ethylene-vinyl acetate copolymers, cellulose acetate butyrate, cellulose acetate propionate, silicone resins, acrylamide resins, epoxy resins, or copolymers and mixtures thereof. Among these, those containing acrylic resins, vinyl chloride resins, cellulose resins, polyester resins, and polyurethane resins are preferred.

[0119] The acrylic resin is not particularly limited as long as it is included as a main component of the monomer constituting the (meth)acrylic acid ester monomer. The acrylic resin may be a homopolymer of one type of radical polymerizable monomer, or a copolymer using two or more types of radical polymerizable monomers selected from each other. In particular, preferred acrylic resins for the non-aqueous ink composition according to this embodiment are a polymer of methyl methacrylate alone, or a copolymer of methyl methacrylate and at least one compound selected from the group consisting of butyl methacrylate, ethoxyethyl methacrylate, and benzyl methacrylate. Examples of commercially available (meth)acrylic resins include "Paraloid B99N," "Paraloid B60," "Paraloid B66," and "Paraloid B82" from Rohm & Haas.

[0120] The vinyl chloride resin may be either a homopolymer composed of vinyl chloride monomers or a copolymer using two or more polymerizable monomers selected from each other. An example of a vinyl chloride polymer is a vinyl chloride-vinyl acetate copolymer resin. A vinyl chloride-vinyl acetate copolymer resin is a polymer of vinyl chloride monomer and vinyl acetate monomer. Examples of vinyl chloride-vinyl acetate copolymer resins include 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 copolymer, and mixtures thereof. The above vinyl chloride-vinyl acetate copolymer resins can be obtained and used from Nisshin Chemical Industry Co., Ltd. under trade names such as "Solvine C," "Solvine CL," "Solvine CNL," "Solvine CLL," "Solvine CLL2," "Solvine C5R," "Solvine TA2," "Solvine TA3," "Solvine A," "Solvine AL," "Solvine TA5R," and "Solvine M5."

[0121] Vinyl chloride-vinyl acetate copolymer resins can be obtained by polymerization of vinyl chloride monomer and vinyl acetate monomer. Any conventionally known polymerization method may be used. The polymerization method is preferably emulsion polymerization or suspension polymerization, and more preferably suspension polymerization.

[0122] Cellulosic resins are resins having a cellulose skeleton obtained by introducing functional groups biologically or chemically from cellulose as a raw material. Examples of celluloseosic resins include cellulose acetate alkylate resins such as cellulose acetate butyrate resin, cellulose acetate propionate resin, and cellulose acetate propionate butyrate resin, as well as cellulose acetate resins, nitrocellulose resins, and mixtures thereof. The above cellulose resins can be obtained and used under product names such as "CAB551-0.01", "CAB551-0.2", "CAB553-0.4", "CAB531-1", "CAB381-0.1", "CAB381-0.5", "CAB381-2", "CAB381-20", "CAP504", and "CAP482-0.5" from EASTMAN.

[0123] Polyester resins are those that contain at least one structural unit obtained by polycondensation of an alcohol component and a carboxylic acid component. Polyester resins may also contain modified polyester resins. Polyester resins can be obtained and used under product names such as "VYLON226", "VYLON270", "VYLON560", "VYLON600", "VYLON630", "VYLON660", "VYLON885", "VYLONGK250", "VYLONGK810", and "VYLON GK890" from Toyobo Co., Ltd., and "elitleUE-3200", "elitleUE-3285", "elitleUE-3320", "elitleUE-9800", and "elitleUE-9885" from Unitika Corporation.

[0124] Polyurethane resins are those that contain at least one structural unit obtained by copolymerizing an alcohol component and an isocyanate component. Polyurethane resins may also include polyurethane resins modified with polyester, polyether, or caprolactone. The above polyurethane resins can be obtained and used under product names such as "Uriano KL-424," "Uriano KL-564," "Uriano KL-593," and "Uriano 3262" from Arakawa Chemical Industries, Ltd., and "Pandex 372E," "Pandex 390E," "Pandex 394E," "Pandex 304," "Pandex 305E," "Pandex P-870," "Pandex P-910," "Pandex P-895," "Pandex 4030," and "Pandex 4110" from DIC Corporation.

[0125] Furthermore, while these acrylic resins, vinyl chloride resins, cellulose resins, polyester resins, and polyurethane resins may be used individually, it is preferable to use a mixture of two types, and more preferably a mixture of acrylic resin and vinyl chloride resin. By adjusting the content ratio of acrylic resin to vinyl chloride resin, it is possible to control the requirements for color development, drying properties, film properties, and printability required for non-aqueous ink compositions. When mixing acrylic resin and vinyl chloride resin, the mixing ratio is not particularly limited and can be changed as appropriate.

[0126] The resin contained in the non-aqueous ink composition is not particularly limited, but it is preferably contained in an amount of 0.05% by mass or more, more preferably in an amount of 0.1% by mass or more, and even more preferably in an amount of 0.5% by mass or more of the total amount of the non-aqueous ink composition. This can further improve the surface drying properties of the resulting recorded material. The resin contained in the non-aqueous ink composition is preferably contained in an amount of 20.0% by mass or less, more preferably in an amount of 15.0% by mass or less, and even more preferably in an amount of 10.0% by mass or less of the total amount of the non-aqueous ink composition. This can more effectively eliminate clogging in the nozzles of the inkjet head and improve the storage stability of the non-aqueous ink composition.

[0127] Furthermore, it is preferable that the resin contained in the non-aqueous ink composition according to this embodiment has an intrinsic viscosity of 90 mL / g or more at 25°C, with the amount of resin being 5% by mass or less of the total resin. This suppresses the occurrence of white spots in areas where solid printing is performed (resulting in good solid filling). Moreover, the non-aqueous ink composition according to this embodiment has high storage stability and high cleaning recovery due to the inclusion of a perinone-based pigment within a predetermined pH range, and furthermore, the amount of resin with an intrinsic viscosity of 90 mL / g or more is 5% by mass or less of the total resin, which more effectively eliminates clogging in the nozzles of the inkjet head, and greatly improves the storage stability, cleaning recovery, and ejection stability of the non-aqueous ink composition.

[0128] In this specification, intrinsic viscosity refers to the specific viscosity [η] obtained after dispersing the target resin in a developing solvent and separating the molecules contained in the resin using a column packed with granular gel in GPC (gel permeation chromatography). SP ]((η-η0) / η0(η0: solvent viscosity, η: solution viscosity)) and concentration C are calculated, and the formula Lim([η SPIn ] / C), the concentration C can be obtained by extrapolating to 0 (C→0). The developing solvent is not particularly limited, but for example, tetrahydrofuran can be used. The same applies to the non-aqueous ink compositions of the second and third embodiments described later.

[0129] Furthermore, the content of resin with an intrinsic viscosity of 90 mL / g or more at 25°C is preferably in the range of 5.0% by mass or less of the total resin, more preferably in the range of 4.0% by mass or less, and even more preferably in the range of 3.0% by mass or less.

[0130] [Surfactants] In the non-aqueous ink composition according to this embodiment, surfactants may be added for the purpose of suppressing the volatilization and solidification of the non-aqueous ink composition in equipment such as nozzles and tubes, preventing solidification, improving resolubility after solidification, reducing surface tension to improve wettability with the recording medium (substrate), suppressing bleeding of the ink composition on the substrate, improving the abrasion resistance of the coating film, and further improving the glossiness of the recorded material. The same applies to the non-aqueous ink compositions of the second and third embodiments described later.

[0131] Among these, it is preferable that the surfactant contains a surfactant having a siloxane skeleton. Pigment A1 tends to aggregate in non-aqueous ink compositions, and the volume-average particle size tends to increase. This can reduce the glossiness of the resulting recorded material. By including a surfactant having a siloxane skeleton in the non-aqueous ink composition according to this embodiment, the glossiness of the resulting recorded material can be improved even if pigment A1 is included. Furthermore, if the non-aqueous ink contains a surfactant having a siloxane skeleton, the ink will bleed less and a recorded material with improved abrasion resistance can be obtained.

[0132] As surfactants having a siloxane skeleton, polyester-modified silicones or polyether-modified silicones are preferred, and specific examples include BYK-313, 315N, 322, 326, 331, 347, 348, BYK-UV3500, 3510, 3530, and 3570 (all manufactured by BYK Chemie Japan).

[0133] Furthermore, the non-aqueous ink composition according to this embodiment may contain a surfactant other than a surfactant having a siloxane skeleton. For example, polyoxyalkylene alkyl ethers such as Nonion 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 Nippon Oil & Fats Co., Ltd.), Emulgen 106, 108, 707, 709, A-90, A-60 (manufactured by Kao Corporation), Floren G-70, D-90, TG-740W (manufactured by Kyoeisha Chemical Co., Ltd.), Poem J-0081HV (manufactured by Riken Vitamin Co., Ltd.), Adecatol NP-620, NP-650, NP-660, NP-675, NP-683, NP-6 Examples of fluorinated surfactants include 86, Adekacol CS-141E, TS-230E (manufactured by Adeka Corporation), Solgen 30V, 40, TW-20, TW-80, Neugen CX-100 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), etc. As for fluorinated surfactants, it is preferable to use fluorinated modified polymers, with specific examples including BYK-340 (manufactured by Bic Chemie Japan Co., Ltd.), etc. Examples of acetylene glycol surfactants include Surfinol® 82, 104, 465, 485, TG (all manufactured by Air Products Japan Co., Ltd.), Orfin® STG, E1010 (all manufactured by Nisshin Chemical Co., Ltd.). The surfactants are not limited to those listed above, and any anionic, cationic, amphoteric, or nonionic surfactant can be used.

[0134] The non-aqueous ink composition according to this embodiment may contain these surfactants together with a surfactant having a siloxane skeleton, or it may contain these surfactants without containing a surfactant having a siloxane skeleton.

[0135] In the non-aqueous ink composition according to this embodiment, the surfactant content is not particularly limited, but the lower limit of the surfactant content is preferably in the range of 0.01% by mass or more, more preferably in the range of 0.05% by mass or more, and even more preferably in the range of 0.1% by mass or more. The lower limit of the surfactant content is preferably in the range of 5.0% by mass or less, more preferably in the range of 4.0% by mass or less, and even more preferably in the range of 3.0% by mass or less.

[0136] [Other ingredients] The non-aqueous ink composition according to this embodiment may optionally contain known additives such as antioxidants, stabilizers such as ultraviolet absorbers, epoxidants, polycarboxylic acids, surface modifiers, leveling agents (acrylic or silicone-based, etc.), defoamers, pH adjusters, bactericides, preservatives, deodorants, charge adjusters, and wetting agents. Specific examples of antioxidants include hindered phenol antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, and hydrazine antioxidants. Specifically, BHA (2,3-butyl-4-oxyanisole) and BHT (2,6-di-t-butyl-p-cresol) are examples. Benzophenone compounds or benzotriazole compounds can be used as ultraviolet absorbers. Furthermore, specific examples of epoxidized compounds include epoxy glycerides, epoxy fatty acid monoesters, and epoxy hexahydrophthalates, with ADEKA O-130P and ADEKA O-180A (manufactured by ADEKA Corporation) being specific examples. Specific examples of polycarboxylic acids include citric acid and maleic acid.

[0137] ≪1-2. Non-aqueous ink composition of the second embodiment≫ The non-aqueous ink composition of the second embodiment according to this embodiment is a non-aqueous ink composition that is ejected by an inkjet method and contains a pigment, a pigment dispersant, and an organic solvent.

[0138] Furthermore, the pigment contained in this non-aqueous ink composition is characterized by containing pigment A2 represented by the following formula (1-2), and the pH of pigment A2 being in the range of 3 to 9.

[0139] [ka] (In formula (1-2), X1 to X10 are independently hydrogen, halogen atom, branched alkyl group having 1 to 5 carbon atoms, aromatic hydrocarbon group which may be substituted with a hydrogen atom, cyano group, nitro group, amino group, -OH, -COOH, -COO) - M + -SO3H, -SO3 - M + , a phthalimide group, a phthalimidemethyl group, or a heterocyclic compound, which may have a hydrogen atom substituted, M + (This indicates a cation.)

[0140] By including pigment A2, whose pH is controlled within the range of 3 to 9, aggregation of pigments can be suppressed in the non-aqueous ink composition, thereby improving storage stability and cleaning recovery.

[0141] Pigment A2 with a pH between 3 and 9 can be obtained by treating the surface of the pigment by washing it with a solution, as described above for pigment A1, or by changing the types of substituents (X1 to X10) in the benzene ring of the structure of formula (1-2), or by applying both treatments. The method for changing the types of substituents (X1 to X10) in the benzene ring is the same as described above for pigment A1. The positions where substituents X1 to X10 are substituted are not particularly limited, as long as the pH of pigment A2 is within the range of 3 to 9, and any of the 10 substitution positions on the benzene ring is acceptable, and the number of substituents is also not particularly limited.

[0142] 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 still more preferably 6 or less. The lower limit of the pH of pigment A2 is preferably 3 or more, and more preferably 4 or more. In particular, when the pH of pigment A2 is 9 or less, the pigment dispersant adheres more easily, making it possible to more effectively suppress the aggregation of pigment A2 in the non-aqueous ink composition. This improves the discharge stability and color stability of the non-aqueous ink composition.

[0143] The preferred range for water content and average particle size of pigment A2 in the non-aqueous ink composition according to this embodiment is the same as the preferred range for water content and average particle size of pigment A1 in the non-aqueous ink composition of the first embodiment described above.

[0144] The preferred range for the content of pigment A2 contained in the non-aqueous ink composition according to this embodiment is the same as the preferred range for the content of pigment A1 in the non-aqueous ink composition of the first embodiment described above. By having a pigment A2 content of 8.0% by mass or less of the total amount of the non-aqueous ink composition, aggregation of pigment A2 in the non-aqueous ink composition can be more effectively suppressed. This makes it possible to relatively increase the content of other additives, and further suppress the increase in viscosity caused by increasing the pigment A2 content, thereby suppressing nozzle clogging of the inkjet head and further improving cleaning recovery performance.

[0145] Examples of pigment A2 represented by formula (1-2) include CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 264, CI Pigment Red 270, CI Pigment Red 272, CI Pigment Red 283, CI Pigment Red 291, CI Pigment Orange 71, CI Pigment Orange 73, CI Pigment Orange 81, and the like.

[0146] Furthermore, pigment A2 represented by formula (1-2) may be synthesized, for example, by treating the surface of a commercially available diketopyrrolopyrrole pigment by washing it with a solution (acidic solution, alkaline solution, or neutral solution), or by changing the types of substituents (X1 to X10) in the benzene ring of the structure of formula (1-2), or by subjecting it to both of these treatments. Commercially available products include BASF's IRGAPHOR RED BT-CF and CROMOPHTAL DPP Red BP (both CI Pigment Red 254), Dainichi Seika Kogyo's Chromofine Red 6156EC (both CI Pigment Red 254), Tokyo Kasei Kogyo's Pigment Red 254 (CI Pigment Red 254), CINIC's Cinilex DPP Red SR-2P (CI Pigment Red 254), BASF's CROMOPHTAL DPP ORANGE TR and IRAGIN ORANGE D2905 (CI Pigment Orange 71), and BASF's Irgazin Orange L 2990 HD (CI Pigment Orange 73).

[0147] The non-aqueous ink composition according to this embodiment may further contain colorants (including pigments and dyes) other than the pigment A2 described above. Examples of such colorants include pigments and dyes with hues similar to pigment A2 (for example, orange, magenta, yellow, and red).

[0148] To illustrate organic pigments using Color Index (CI) numbers, we have CI 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, and CI Pigment Red 5, 7, 9, 12, 48, 49, 52, Examples include 53, 57:1, 97, 112, 122, 123, 146, 149, 150, 168, 177, 180, 184, 192, 202, 206, 208, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 238, 240, 269, 291, CI Pigment Orange 16, 36, 43, 51, 55, 59, 61, 64, C.I. Pigment Violet 19, 23, 29, 30, 37, 40, 50, CI Pigment Brown 23, 25, 26, etc.

[0149] Furthermore, a dispersion aid (pigment derivative), described later, may be used in conjunction with the pigment dispersant. This can improve the dispersion stability of the pigment.

[0150] Next, we will describe each component contained in the non-aqueous ink composition according to this embodiment.

[0151] [Organic solvents] The 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 from the viewpoint of dispersing the pigment containing pigment A2 and more effectively achieving the effects of the present invention, it is preferable that it contains organic solvent B (at least one selected from the group consisting of alkylamide solvents (b1), cyclic amide solvents (b2), and lactone solvents (b3)).

[0152] For example, if a glycol ether-based solvent, as described later, is included as the organic solvent, the affinity between the glycol ether-based solvent and "pigment A2" is poor, which can cause pigment A2 to aggregate in the non-aqueous ink composition, resulting in poor cleaning recovery. Therefore, by including organic solvent B (at least one selected from the group consisting of alkylamide-based solvents (b1), cyclic amide-based solvents (b2), and lactone-based solvents (b3)), the deterioration of cleaning recovery due to the aggregation of pigment A2 can be effectively suppressed. For this reason, the organic solvent included in the non-aqueous ink composition of the present invention is not particularly limited, but in particular, when a glycol ether-based solvent is included, including organic solvent B (at least one selected from the group consisting of alkylamide-based solvents (b1), cyclic amide-based solvents (b2), and lactone-based solvents (b3)) together with the glycol ether-based solvent results in a non-aqueous ink composition with high storage stability and high cleaning recovery.

[0153] The preferred types of solvents in the alkylamide solvent (b1), cyclic amide solvent (b2), and lactone solvent (b3) are the same as those in the non-aqueous ink composition of the first embodiment described above.

[0154] The content of the cyclic amide solvent (b2) is not particularly limited, but the lower limit of the content of the cyclic amide solvent (b2) is preferably in the range of 1% by mass or more, more preferably in the range of 10% by mass or more, and even more preferably in the range of 15% by mass or more, based on the total amount of the non-aqueous ink composition. The preferred content ranges for the alkylamide solvent (b1), cyclic amide solvent (b2), and lactone solvent (b3) contained in the non-aqueous ink composition other than the "lower limit of the content of the cyclic amide solvent (b2)" are the same as those for the alkylamide solvent (b1), cyclic amide solvent (b2), and lactone solvent (b3) in the non-aqueous ink composition of the first embodiment described above.

[0155] Among the organic solvents B, it is preferable that they contain either an alkylamide solvent (b1) or a cyclic amide solvent (b2), with the alkylamide solvent (b1) being more preferable. Organic solvent B is sufficiently effective when it contains at least one of the alkylamide solvent (b1), cyclic amide solvent (b2), or lactone solvent (b3), but two or more types of solvents may be mixed from among the organic solvents B. When two or more types of organic solvent B are mixed, the preferred range for the total content of organic solvent B contained in the non-aqueous ink composition is the same as that of the non-aqueous ink composition of the first embodiment described above.

[0156] [Other organic solvents] The non-aqueous ink composition according to this embodiment may contain organic solvents other than the organic solvent B described above. Specifically, examples include glycol ether dialkyls in which the OH groups at both ends of the glycol are alkyl-substituted, glycol ether monoalkyls in which one of the OH groups 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, tetrahydric alcohols, alkanolamines, etc.). The preferred types of other organic solvents are the same as those in the non-aqueous ink composition of the first embodiment described above, including glycol ether dialkyls, glycol ether monoalkyls, and carbonate esters. The preferred range for the total content of other organic solvents contained in the non-aqueous ink composition is the same as that of the non-aqueous ink composition of the first embodiment described above.

[0157] [Pigment dispersant] In the non-aqueous ink composition according to this embodiment, a dispersant may be used as needed. The preferred type of pigment dispersant is the same as that of the pigment dispersant in the non-aqueous ink composition of the first embodiment described above.

[0158] In particular, in the non-aqueous ink composition according to this embodiment containing 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. Among these, it is preferable to use a pigment dispersant with an amine value in the range of 20 mg KOH / g to 100 mg KOH / g.

[0159] The preferred range for the content of the pigment dispersant contained in the non-aqueous ink composition is the same as that of the non-aqueous ink composition of the first embodiment described above.

[0160] [Dispersing agent] In the non-aqueous ink composition according to this embodiment, a dispersion aid may be used as needed.

[0161] [resin] The non-aqueous ink composition according to this embodiment does not necessarily contain a resin, but it may contain one. The preferred type of resin is the same as the resin in the non-aqueous ink composition of the first embodiment described above. The resin content in the non-aqueous ink composition and the preferred range of resins with an intrinsic viscosity of 90 mL / g or more at 5°C are the same as those in the non-aqueous ink composition of the first embodiment described above.

[0162] [Surfactants] The non-aqueous ink composition according to this embodiment may also contain a surfactant.

[0163] Examples of 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 Nippon Oil & Fats Co., Ltd.), Emulgen 106, 108, 707, 709, A-90, A-60 (manufactured by Kao Corporation), and F Lauren G-70, D-90, TG-740W (manufactured by Kyoeisha Chemical Co., Ltd.), Poem J-0081HV (manufactured by 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 CX-100 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) As fluorine-based surfactants, it is preferable to use fluorine-modified polymers, such as BYK-340 (manufactured by BIC Chemie Japan Co., Ltd.). As silicone-based surfactants having a siloxane skeleton, it is preferable to use polyester-modified silicone or polyether-modified silicone, such as BYK-313, 315N, 322, 326, 331, 347, 348, BYK-UV3500, 3510, 3530, 3570 (all manufactured by BIC Chemie Japan Co., Ltd.). As acetylene glycol-based surfactants, examples include Surfinol® 82, 104, 465, 485, TG (all manufactured by Air Products Japan Co., Ltd.), Orfin® STG, E1010 (all manufactured by Nisshin Chemical Co., Ltd.).

[0164] The surfactant is not limited to those mentioned above, and any anionic, cationic, amphoteric, or nonionic surfactant can be used. Among these, it is preferable that the surfactant contains a surfactant having a siloxane skeleton. If a non-aqueous ink contains a surfactant having a siloxane skeleton, the ink will bleed less and a record with improved abrasion resistance can be obtained. The same applies to the non-aqueous ink composition of the third embodiment described later.

[0165] The range of surfactant content contained in the non-aqueous ink composition is the same as that of the non-aqueous ink composition of the first embodiment described above.

[0166] [Other ingredients] The non-aqueous ink composition according to this embodiment may contain other components as optional components. The types of other components contained in the non-aqueous ink composition are the same as those in the non-aqueous ink composition of the first embodiment described above.

[0167] ≪1-3. Non-aqueous ink composition of the third embodiment≫ The non-aqueous ink composition according to this embodiment is a non-aqueous ink composition that is ejected by an inkjet method and contains a pigment, a pigment dispersant, and an organic solvent.

[0168] Furthermore, this non-aqueous ink composition is characterized by containing halogenated phthalocyanine pigment A3 as the pigment and organic solvent B as the organic solvent described below.

[0169] Organic solvent B: At least one selected from the group consisting of alkylamide solvents (b1), cyclic amide solvents (b2), and lactone solvents (b3).

[0170] Halogenated phthalocyanine pigment A3 is a compound in which at least some of the hydrogen atoms in the benzene ring of the phthalocyanine skeleton are replaced by halogen atoms (fluorine, chlorine, bromine, iodine).

[0171] [ka] (In formulas (1-3), 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 ligands.)

[0172] Halide phthalocyanine pigments are pigments in which a maximum of 16 halogen atoms are bonded to each phthalocyanine molecule.

[0173] When phthalocyanine pigments are halogenated, they become green pigments. Generally, to represent green in recordings, one of the following methods can be considered: (I) using green ink made from green pigment, (II) using green ink made from yellow and blue pigments, or (III) representing green with two colors: yellow ink made from yellow pigment and cyan ink made from blue pigment. Of these, (II), which uses multiple pigments, and (III), which uses multiple inks, end up representing green with yellow and blue pigments, so the saturation tends to decrease. On the other hand, in (I), since green ink made from green pigment that is inherently green is used without using multiple pigments or multiple inks, the saturation is improved compared to methods (II) and (III), and color reproduction can be improved.

[0174] Furthermore, phthalocyanine pigments generally have higher weather resistance than yellow pigments. Therefore, by using green ink containing halogenated phthalocyanine pigments, the weather resistance of the resulting recordings can be improved compared to methods (II) and (III) that use yellow and blue pigments.

[0175] However, because halogenated phthalocyanine pigment A3 has a substituted halogen element, the overall density of the pigment (weight per unit volume) is high, making it difficult to disperse it in a non-aqueous ink composition for a long period of time. Therefore, our research has revealed that when a non-aqueous ink composition containing halogenated phthalocyanine pigment is stored for a long period of time, the pigment precipitates within the non-aqueous ink composition, reducing storage stability, color stability, and cleaning recovery.

[0176] Therefore, by including organic solvent B (at least one selected from the group consisting of alkylamide solvents (b1), cyclic amide solvents (b2), and lactone solvents (b3)), storage stability, color stability, and cleaning recovery properties can be improved.

[0177] The preferred range of water content in the non-aqueous ink composition according to this embodiment is the same as the preferred range of water content in the non-aqueous ink composition of the first embodiment described above. Because pigment A3 is highly hydrophobic, non-aqueous inkjet compositions containing this pigment tend to deteriorate relatively easily upon contact with water, leading to poor storage stability. In addition to containing organic solvent B, reducing the water content in the non-aqueous ink composition to minimize water content (intentionally omitting water) makes it possible to more effectively suppress the precipitation of halogenated phthalocyanine pigment A3, thereby more effectively improving storage stability and ejection stability.

[0178] The following describes each component included in the non-aqueous ink composition according to this embodiment.

[0179] [Pigments] The non-aqueous ink composition according to this embodiment contains halogenated phthalocyanine pigment A3. Halogenated phthalocyanine pigment A3 is a compound having a phthalocyanine skeleton as shown in the following formula.

[0180] [ka] (In formulas (1-3), 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 ligands.)

[0181] A halogenated phthalocyanine pigment is one in which at least one of X1 to X16 is replaced by a halogen atom. In other words, a halogenated phthalocyanine pigment is a pigment in which a minimum of 1 halogen atom and a maximum of 16 halogen atoms are bonded to each phthalocyanine molecule. The more halogen groups a halogenated phthalocyanine pigment has, the closer the pigment is to green. The number of halogen atoms substituted in a 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.

[0182] The phthalocyanine halide pigment A3 may have a central M in its phthalocyanine skeleton consisting of two hydrogen atoms, or it may be a metal halide phthalocyanine pigment where M is a metal atom. When 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) are particularly desirable. Furthermore, when M is a metal atom, M may have a ligand.

[0183] Examples of such halogenated phthalocyanine pigments A3 (including metal halide phthalocyanine pigments) include CI Pigment Green 7, 36, 58, 59, 62, and 63. The halogenated phthalocyanine pigment A3 may be manufactured by conventionally known methods, or it may be a commercially available product such as DIC's FASTGEN GREEN 2YK (CI Pigment Green 36), Dainichi Seika Kogyo's Cyanine Green 5370 (CI Pigment Green 36), DIC's FASTGEN GREEN 5740 (CI Pigment Green 7), or DIC's Fastogen GREEN A110 (CI Pigment Green 58).

[0184] The volume-based cumulative 50% particle size (D50) of pigment A3 is not particularly limited, but the lower limit of the volume-based cumulative 50% particle size (D50) is preferably 30 nm or more, more preferably 40 nm or more, and even more preferably 50 nm or more. This improves the weather resistance of halogenated phthalocyanine pigment A3. The upper limit of the volume-based cumulative 50% particle size (D50) is preferably 150 nm or less, more preferably 140 nm or less, and even more preferably 130 nm or less. This more effectively suppresses the precipitation of halogenated phthalocyanine pigment A3 in the non-aqueous ink composition, improving color stability.

[0185] 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, and even more preferably 70 nm or more. This improves the weather resistance of halogenated phthalocyanine pigment A3. The upper limit of the volume-based cumulative 90% particle size (D90) is preferably 300 nm or less, more preferably 290 nm or less, and even more preferably 280 nm or less. This more effectively suppresses the precipitation of halogenated phthalocyanine pigment A3 in the non-aqueous ink composition, improving color stability.

[0186] The content of pigment A3 is not particularly limited, but the lower limit of the pigment A3 content is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and still more preferably 1.5% by mass or more, of the total amount of the non-aqueous ink composition. This ensures sufficient print density and improves the color reproducibility of the recorded material. The upper limit of the pigment A3 content is preferably 8.0% by mass or less, more preferably 6.0% by mass or less, and still more preferably 5.0% by mass or less, of the total amount of the non-aqueous ink composition. This allows for a relative increase in the content of other additives, and further suppresses the increase in viscosity caused by increasing the pigment (halogenated phthalocyanine pigment) content, thereby suppressing nozzle clogging of the inkjet head and further improving cleaning recovery.

[0187] The non-aqueous ink composition according to this embodiment may further contain colorants (including pigments and dyes) other than the halogenated phthalocyanine pigment A3 described above. Examples of such colorants include pigments and dyes with a similar structure and hue (cyan, green, yellow) to halogenated phthalocyanine pigment A3.

[0188] Examples of organic pigments using Color Index (CI) numbers include CI Pigment Blue 15, 15:1, 15:3, 15:4, 15:6, 16, 22, 60, 64, CI 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, and other pigments.

[0189] Furthermore, a dispersion aid (pigment derivative) described later may be used in conjunction with the pigment dispersant. This improves the dispersion stability of the pigment and enhances the storage stability of the non-aqueous ink composition.

[0190] Next, we will describe each component contained in the non-aqueous ink composition according to this embodiment.

[0191] [Organic solvents] The 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 solvents (b1), cyclic amide solvents (b2), and lactone solvents (b3)).

[0192] Our research has revealed that by including an alkylamide solvent (b1), it becomes possible to disperse halogenated phthalocyanine pigment A3 in a non-aqueous ink composition for a long period of time, thereby improving storage stability, color stability, and cleaning recovery. Although the reason for this is not entirely clear, it is thought that the affinity of halogenated phthalocyanine pigment A3 with the pigment dispersant improves, allowing for effective dispersion in a non-aqueous ink composition containing an alkylamide solvent, thereby suppressing the precipitation of halogenated phthalocyanine pigment A3.

[0193] Furthermore, our research has revealed that by including a cyclic amide solvent (b2) or a lactone solvent (b3), it is possible to disperse halogenated phthalocyanine pigment A3 in a non-aqueous ink composition for a long period of time, thereby improving storage stability, color stability, and cleaning recovery.

[0194] The preferred types of solvents in the alkylamide solvent (b1), cyclic amide solvent (b2), and lactone solvent (b3) are the same as those in the non-aqueous ink composition of the first embodiment described above.

[0195] Among the organic solvents B, it is preferable that they contain either an alkylamide solvent (b1) or a cyclic amide solvent (b2), with the alkylamide solvent (b1) being more preferable. Organic solvent B is sufficiently effective when it contains at least one of the alkylamide solvent (b1), cyclic amide solvent (b2), or lactone solvent (b3), but two or more types of solvents may be mixed from among the organic solvents B. When two or more types of organic solvent B are mixed, the preferred range for the total content of organic solvent B contained in the non-aqueous ink composition is the same as that of the non-aqueous ink composition of the first embodiment described above.

[0196] [Other organic solvents] The non-aqueous ink composition according to this embodiment may contain organic solvents other than the organic solvent B described above. Specifically, examples include glycol ether dialkyls in which the OH groups at both ends of the glycol are alkyl-substituted, glycol ether monoalkyls in which one of the OH groups 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, tetrahydric alcohols, alkanolamines, etc.). The preferred types of other organic solvents are the same as those in the non-aqueous ink composition of the first embodiment described above, including glycol ether dialkyls, glycol ether monoalkyls, and carbonate esters. The preferred range for the total content of other organic solvents contained in the non-aqueous ink composition is the same as that of the non-aqueous ink composition of the first embodiment described above.

[0197] [Pigment dispersant] In the non-aqueous ink composition according to this embodiment, a pigment dispersant may be used as needed. In particular, in the non-aqueous ink composition according to this embodiment containing pigment A3, it is preferable to use a pigment dispersant having a basic group. Furthermore, by using a pigment dispersant having a basic group, aggregation of halogenated phthalocyanine pigment A3 in the non-aqueous ink composition can be suppressed more effectively. The preferred type of pigment dispersant is the same as that of the pigment dispersant in the non-aqueous ink composition of the first embodiment described above.

[0198] Among these, it is preferable to use a pigment dispersant with an amine value in the range of 20 mg KOH / g to 100 mg KOH / g. This can further effectively suppress the aggregation of pigment A3 in the non-aqueous ink composition.

[0199] The preferred range for the content of the pigment dispersant contained in the non-aqueous ink composition is the same as that of the non-aqueous ink composition of the first embodiment described above.

[0200] [Dispersing agent] In the non-aqueous ink composition according to this embodiment, a dispersion aid may be used as needed.

[0201] [resin] The non-aqueous ink composition according to this embodiment does not necessarily contain a resin, but it may contain one. The preferred type of resin is the same as the resin in the non-aqueous ink composition of the first embodiment described above. The preferred range of resin content in the non-aqueous ink composition is the same as the non-aqueous ink composition of the first embodiment described above.

[0202] Furthermore, it is preferable that the resin contained in the non-aqueous ink composition according to this embodiment has an intrinsic viscosity of 90 mL / g or more at 25°C, with the amount of resin being 5% by mass or less of the total resin. This results in superior printing performance, such as continuous ejection stability, and further effectively improves the cleaning recovery properties of the resulting recorded material.

[0203] Furthermore, the content of resin with an intrinsic viscosity of 90 mL / g or more at 25°C is preferably 4.0% by mass or less of the total resin, more preferably 3.5% by mass or less, and even more preferably 2.5% by mass or less.

[0204] [Surfactants] The non-aqueous ink composition according to this embodiment may contain a surfactant. The preferred type of surfactant is the same as that of the non-aqueous ink composition in the second embodiment described above. The preferred range of surfactant content in the non-aqueous ink composition is the same as that of the non-aqueous ink composition in the second embodiment described above.

[0205] [Other ingredients] The non-aqueous ink composition according to this embodiment may contain other components as optional components. The types of other components contained in the non-aqueous ink composition are the same as those in the non-aqueous ink composition of the first embodiment described above.

[0206] ≪2. Method for producing non-aqueous ink compositions≫ The non-aqueous ink composition according to this embodiment can be manufactured by mixing an organic solvent, a pigment containing pigment A1 or A2, and other components (e.g., resin) using a paint shaker. In this case, the components may be dispersed using zirconia beads. Furthermore, the obtained non-aqueous ink composition may be adjusted to the desired dissolved oxygen and dissolved nitrogen content by degassing treatment as needed.

[0207] Furthermore, when using a pigment containing pigment A3, it can be manufactured by mixing an organic solvent containing organic solvent B (at least one selected from the group consisting of alkylamide solvents (b1), cyclic amide solvents (b2), and lactone solvents (b3)), a pigment containing halogenated phthalocyanine pigment A3, and other components (e.g., resin) using a paint shaker.

[0208] The non-aqueous ink compositions according to this embodiment (the non-aqueous ink compositions of the first, second, and third embodiments) are non-aqueous ink compositions that do not intentionally contain water, but moisture may be mixed in from the raw materials and during the manufacturing process. It is desirable that the moisture content in the non-aqueous ink composition be as low as possible. If there is an excessive amount of moisture, storage stability and discharge performance will be poor, and the risk of solid components etc. will increase. The upper limit of the moisture content in the non-aqueous ink composition is preferably 5.0% by mass or less of the total amount of the non-aqueous ink composition, more preferably 1.0% by mass or less, and particularly preferably 0.5% by mass or less.

[0209] In this case, it is preferable to dry the organic solvent beforehand. By drying the organic solvent beforehand, the amount of water contained in the non-aqueous composition can be reduced. Methods for drying the organic solvent include, for example, spraying an inert gas (e.g., nitrogen gas) dried under an inert gas atmosphere such as nitrogen for a predetermined time, distilling and purifying the organic solvent, permeating the organic solvent through a semipermeable membrane that selectively permeates water, or selectively adsorbing water mixed in the organic solvent with a water adsorbent that adsorbs water.

[0210] ≪3. Recording Method Using Ink Composition≫ The recording method according to this 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. Among the above non-aqueous ink compositions, the non-aqueous ink compositions of the first and second embodiments contain Pigment A1 or A2 in which the substituents in the structure are changed so that the pH is within the range of 3 or more and 9 or less, thereby satisfying the properties required for the non-aqueous ink composition ejected by the inkjet method. Also, in the recording method according to this embodiment, it satisfies the properties required for the non-aqueous ink composition ejected by the inkjet method. Among the above non-aqueous ink compositions, the non-aqueous ink composition of the third embodiment contains a halogenated phthalocyanine pigment A3 and has high storage stability and color tone stability. Also, the recorded matter obtained by using the recording method according to this embodiment has high color tone stability. The method of ejecting by the inkjet method may be a piezo method using a piezoelectric element or a thermal method using a heating element, and is not particularly limited.

[0211] ≪4. Method for manufacturing a recorded matter≫ The recording method using the above ink composition can also be defined as a method for manufacturing a recorded matter. By manufacturing a recorded matter using the non-aqueous ink composition of the first embodiment among the above non-aqueous ink compositions, the recorded matter can be manufactured in a state that satisfies the properties required for the non-aqueous ink composition ejected by the inkjet method. Also, by manufacturing a recorded matter using the non-aqueous ink composition of the second embodiment among the above non-aqueous ink compositions, the recorded matter can be manufactured in a state that satisfies the properties of high storage stability and high cleaning recovery property. Also, by manufacturing a recorded matter using the non-aqueous ink composition of the third embodiment among the above non-aqueous ink compositions, a recorded matter with high color tone stability can be obtained.

[0212] ≪5. Recorded matter≫ Each layer constituting the recorded matter manufactured by the manufacturing method of the recorded matter of the above-described embodiment will be described.

[0213] [Medium (recording medium)] The substrate (recording medium) that can be used in the recording method according to this embodiment is not particularly limited, and may be a non-absorbent substrate such as a resin substrate, metal, or glass plate, an absorbent substrate such as paper or cloth, or a substrate with a surface coating such as a substrate with a receiving layer, and various substrates can be used.

[0214] Among these, the above-mentioned non-aqueous ink composition is preferable because, since it does not contain water, its surface is preferably made primarily of resin. In particular, when the above-mentioned non-aqueous ink composition contains an alkylamide solvent (b) that penetrates the resin substrate, the bleeding of printing on a medium (recording medium) whose surface is made of resin is reduced, and the printing becomes clearer. Examples of resins include polyvinyl chloride polymers, acrylic, PET, polycarbonate, PE, PP, etc. It may also be used in resin substrates (so-called resin substrates for lamination) that are intended to be laminated to the recording surface of the recording material. In particular, substrates (recording media) whose surface is made of hard or flexible polyvinyl chloride polymer are preferred. Examples of substrates (recording media) whose surface is made of polyvinyl chloride polymer include polyvinyl chloride substrates (films or sheets).

[0215] [Recording layer] The recording layer (also called the printing layer) is a layer formed by the volatilization of the solvent contained in the above-mentioned non-aqueous ink composition, and is the layer that forms the desired image. By ejecting the non-aqueous ink composition of the first embodiment among the above-mentioned non-aqueous ink compositions, the characteristics required for a non-aqueous ink composition ejected by an inkjet method are met. The non-aqueous ink composition of the second embodiment among the above-mentioned non-aqueous ink compositions has high storage stability and high cleaning recovery properties, so it is possible to form the desired image even with a non-aqueous ink composition that has been stored for a long period of time. By ejecting the non-aqueous ink composition of the third embodiment among the above-mentioned non-aqueous ink compositions, a recording layer with high color stability is obtained. Furthermore, since the above-mentioned non-aqueous ink composition has high storage stability, it is possible to form the desired image even with a non-aqueous ink composition that has been stored for a long period of time.

[0216] [Other layers] The recording material according to this embodiment may further have a layer having a desired function on the upper surface of the recording layer (printing layer). For example, an overcoat layer containing at least one of a resin and a wax may be formed to further impart scratch resistance and gloss to the recording material. Alternatively, a layer expressing a textured surface (matte surface) may be formed by including a filler or by varying the film thickness on a pixel-by-pixel basis. Furthermore, to impart weather resistance to the recording material, a weather-resistant layer containing an ultraviolet absorber or a light stabilizer, or a glossy layer containing a glossy pigment, may be formed.

[0217] ≪6. Ink Set≫ The ink set according to this embodiment is an ink set comprising at least the above-mentioned non-aqueous ink composition. For example, if the above-mentioned non-aqueous ink composition is red ink, orange ink, or green ink, combining it with conventionally known yellow ink, magenta ink, cyan ink, or black ink will not only achieve the effects of the present invention but also expand the range of color reproducibility.

[0218] Furthermore, the above-mentioned non-aqueous ink composition may be used as an ink set containing a white ink, metallic ink, pearl ink, or other glossy ink, or as an ink set containing a clear ink that does not contain pigment.

[0219] ≪7. Inkjet Recording Devices≫ Conventional inkjet recording devices can be used to eject the above-mentioned non-aqueous ink composition by the inkjet method. For example, inkjet printers such as the VersaArt RE-640 or those manufactured by Roland DG Corporation can be used.

[0220] As an example of the configuration of an inkjet recording device, an on-carriage type serial printer type inkjet recording device will be described. However, an inkjet recording device capable of implementing the recording method according to this embodiment may be an off-carriage type inkjet recording device in which the ink cartridge is fixed externally, or a line printer type inkjet recording device in which the inkjet head ejects the ink composition onto the recording medium (substrate) without moving.

[0221] Furthermore, it is preferable that the inkjet recording device includes a heating mechanism and a fixing mechanism for fixing the substrate. By controlling the substrate surface temperature with the heating mechanism provided in the inkjet recording device, the non-aqueous ink composition that has landed on the substrate (recording medium) is dried, making it possible to volatilize the organic solvent contained in the non-aqueous ink composition.

[0222] Furthermore, the fixing mechanism that secures the substrate allows the non-aqueous ink composition to be dried while the substrate (recording medium) is fixed, suppressing uneven heat distribution caused by the substrate bending due to heating. This makes it possible to effectively dry the non-aqueous ink composition that has landed on the substrate (recording medium).

[0223] The heating mechanism provided in the inkjet recording device may be a preheater, platen heater, afterheater, etc., or it may be a mechanism that blows warm air onto the recording material. Alternatively, multiple heating mechanisms may be combined.

[0224] The surface temperature of the substrate heated by the heating mechanism is not particularly limited as long as it can volatilize the organic solvent contained in the non-aqueous ink composition. The lower limit of the substrate surface temperature is preferably 20°C or higher, more preferably 30°C or higher, and even more preferably 40°C or higher. The upper limit of the substrate surface temperature is preferably 70°C or lower, more preferably 60°C or lower, and even more preferably 50°C or lower.

[0225] The fixing mechanism for securing the substrate is not particularly limited and may be a fixing mechanism that secures the substrate with a predetermined jig, or a fixing mechanism that uses negative pressure to attract and adsorb the substrate.

[0226] The inkjet head that ejects the above-mentioned non-aqueous ink composition may be a piezo-type inkjet head using a piezoelectric element or a thermal-type inkjet head using a heating element, and is not particularly limited.

[0227] Furthermore, the inkjet recording device may be configured to connect a container (such as an ink cartridge or bottle) for storing the non-aqueous ink composition with an inkjet discharge port for dispensing the non-aqueous ink composition, and to include a plastic tube through which the non-aqueous ink composition flows, so that the non-aqueous ink composition is supplied to the inkjet head through this plastic tube and dispensed by the inkjet method.

[0228] If the pigments A1 (perinone pigment), A2 (diketopyrrolopyrrole pigment), and A3 (halogenated phthalocyanine pigment) contained in the above-mentioned non-aqueous ink composition aggregate within the plastic tube, the nozzle may become clogged, and the ejection stability may decrease. Therefore, it is preferable that the inkjet recording device according to this embodiment be equipped with a mechanism that can resolve nozzle clogging. In addition to using a perinone pigment or diketopyrrolopyrrole pigment within a predetermined pH range, the effects of the present invention are further enhanced by providing a mechanism that can resolve nozzle clogging.

[0229] Specifically, it is preferable that the tube connected to the storage mechanism and the inkjet ejection port is equipped with a valve mechanism to adjust the flow path of the non-aqueous ink composition. By supplying the non-aqueous ink composition from the storage mechanism to the inkjet ejection port via the valve mechanism, the ejection stability of the non-aqueous ink composition can be further improved.

[0230] The material of the plastic tube is not particularly limited, and examples thereof include polyolefin resins such as polyethylene resins, ethylene propylene diene rubber, nylon, polyurethane, PTFE, and the like. Among these, polyethylene resins and ethylene propylene diene rubber are preferred.

[0231] Also, the inkjet recording apparatus according to the present embodiment can be used for inks of various colors such as yellow, magenta, cyan, black, etc., and also for light magenta, light cyan, light black, orange, green, red, white, etc. The order of the colors to be printed, the position and configuration of the head are not particularly limited. Further, the inkjet recording apparatus according to the present embodiment may or may not include a winding mechanism for the recording medium (substrate), a drying mechanism for drying the surface of the substrate, and an ink circulation mechanism.

Example

[0232] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these descriptions in any way.

[0233] (First Embodiment) 1. Preparation of Resin (1) Acrylic Resin A mixture of 150 g of methyl methacrylate, 50 g of butyl methacrylate and a predetermined amount of t-butylperoxy-2-ethylhexanoate (polymerization initiator) was dropped into 300 g of diethylene glycol diethyl ether maintained at 100°C over 1.5 hours. After completion of the dropping, the reaction was carried out 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. At this time, the amount of t-butylperoxy-2-ethylhexanoate as the polymerization initiator was changed to control the polymerization average molecular weight of methyl methacrylate (acrylic resin) to be 30,000 to 105,000 (the mass of the polymerization initiator used at this time is described in Table 1 below. It is denoted as "initiator amount" in Table 1).

[0234] (2) Vinyl chloride-vinyl acetate copolymer resin In an autoclave equipped with a stirring device, after purging with nitrogen, 100 parts deionized water, 40 parts methanol, 32 parts vinyl chloride, 5 parts vinyl acetate, 0.2 parts glycidyl methacrylate, 3.55 parts hydroxypropyl acrylate, 0.1 part hydroxypropyl methylcellulose (suspending agent), 0.026 parts di-2-ethylhexyl peroxydicarbonate (polymerization initiator), and a predetermined amount of di-3,5,5-trimethylhexanol peroxide (polymerization initiator) were charged. The mixture was heated to 63°C while stirring under a nitrogen gas atmosphere. Immediately after reaching 63°C, 48 parts vinyl chloride was continuously injected over 6 hours, and a mixture of 0.6 parts glycidyl methacrylate and 10.65 parts hydroxypropyl acrylate was continuously injected over 5.4 hours to induce a copolymerization reaction. When the internal pressure of the autoclave reached 0.3 MPa, the remaining pressure was released, the mixture was cooled, and the resin slurry was extracted, filtered, and dried to obtain a vinyl chloride copolymer resin. At this time, the amount of di-3,5,5-trimethylhexanol peroxide, which is the polymerization initiator, was changed to control the average polymerization molecular weight of the vinyl chloride-vinyl acetate copolymer resin to be between 40,000 and 75,000 (the mass of the polymerization initiator used at this time is listed in Table 1 below. In Table 1, it is labeled as "Amount of Initiator").

[0235] (3) Cellulose resins Commercially available cellulose-based resins (EASTMAN CHEMICAL's CAB551-0.01, CAB553-0.4, and CAP482-0.5) were used.

[0236] (4) Polyester 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 parts by mass of tetrabutyl titanate were placed in a round-bottom flask, and the temperature was gradually raised to 240°C over 4 hours while removing the distillate from the system to carry out the esterification reaction. After the completion of the esterification reaction, the pressure was reduced to 10 mmHg over 30 minutes, and the temperature was raised to 250°C to carry out initial polymerization. Subsequently, late polymerization was carried out at a pressure of 1 mmHg or less for 1 hour to obtain a polyester resin.

[0237] (5) Polyurethane resin 192.5 parts by mass of polycarbonate diol (Praxel CD-220: manufactured by Daicel), 41.6 parts by mass of isophorone diisocyanate (IPDI: manufactured by Evonik), and 100 parts by mass of N,N-diethylformamide (DEF) were placed in a round-bottom flask and mixed uniformly. Then, a mixture of 0.01 parts by mass of T100BHJ (catalyst) and 0.09 parts by mass of N,N-diethylformamide (DEF) was added and reacted at 75°C for 3 hours to obtain a prepolymer having isocyanate groups at the ends. 250 parts by mass of N,N-diethylformamide (DEF) were added and uniformly dissolved. Then, a chain extension solution prepared by dissolving 12 parts by mass of 3-aminomethyl3,5,5-trimethylcyclohexylamine (IPD: manufactured by Evonik) in 100 parts by mass of DEF was added and the mixture was stirred at 60°C for a further 40 minutes. Subsequently, a reaction stopper was added, consisting of 3.8 parts by mass of monoisopropanolamine (MIPA: manufactured by Daicel) dissolved in 50 parts by mass of N,N-diethylformamide (DEF). Finally, 250 parts by mass of N,N-diethylformamide (DEF) were added to obtain a polyurethane solution with a solid content of 25.0% by mass.

[0238] 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 percentage of resins with an intrinsic viscosity of 90 mL / g or higher at 25°C. The weight-average molecular weight (relative molecular mass) was measured by GPC (gel permeation chromatography). The percentage of resins with an intrinsic viscosity of 90 mL / g or higher was determined by connecting a viscometer (WYATT ViscoStar III) and a refractive index detector (WYATT Optilab T-rEX) to a Shimadzu SEC(GPC) system, using tetrahydrofuran as the developing solvent. First, the sample was passed through a column heated to 40°C in the Shimadzu SEC(GPC) system, and then the pass-through was cooled to 25°C. The specific viscosity [η] was measured using the viscometer. SP [η] is determined, and the concentration C is determined using a refractive index detector. Lim([η] SP In the formula ] / C), the intrinsic viscosity was determined by extrapolating the concentration C to 0.

[0239] [Table 1]

[0240] 2. Synthesis of Pigment A1 Synthesized pigments A1 1-6 were synthesized under the conditions described in Table 2. Specifically, 2 parts by mass of the perinone-based pigment (a1) in Table 2 were dispersed in the solvent (a2) in Table 2, and (a3) ​​in (a4) parts of (a4) in Table 2 were added. After stirring for (a6) hours at the temperature conditions (a5) in Table 2, synthetic pigments 1 and 2 were washed with ethanol and water, and synthetic pigments 3, 4, and 6 were washed with water to obtain synthetic pigments A1 1-6. In Table 2, pigment Ap (synthesized pigment 5) is a pigment synthesized by the method described in Japanese Patent No. 3076738 and is pigment A1 represented by formula (1-1). Synthesized pigment 5 was not subjected to the solvent dispersion treatment.

[0241] [Table 2] (In the table, "none" in (a3) ​​and (a4) means that no substituent agent was added.)

[0242] The pH of synthetic products 1-6 of pigment A1 was measured according to the test method of JIS K5101-17-1:2004 (as shown in (a7) of Table 2).

[0243] 3. Preparation of non-aqueous ink composition Non-aqueous ink compositions for the examples and comparative examples were prepared with each component in the proportions shown in the table below, according to the respective organic solvents, resins, dispersants, and pigments (colorants). Specifically, the non-aqueous ink compositions were prepared by dispersing each component with zirconia beads using a paint shaker. The unit is mass%. The particle size of the zirconia beads and the dispersion time are listed in Tables 3 to 10 below.

[0244] Furthermore, the volume-based cumulative 90% particle size (D90) of the pigments contained in the non-aqueous ink composition was measured using a particle size distribution analyzer (NANOTRACWAVE particle size analyzer manufactured by Microtrac Bell Co., Ltd.).

[0245] 4. Evaluation (Storage stability) The storage stability of the non-aqueous ink compositions of the examples, comparative examples, and reference examples was evaluated. Specifically, the non-aqueous ink compositions were stored at 60°C for one month, and the changes in viscosity and the volume-based cumulative 50% particle size (D50) of the pigment before and after the test were observed. The storage stability was evaluated according to the following criteria. The viscosity of the ink was measured at 20°C using a falling-ball viscometer (AMVn, Anton Paar), and the volume-based cumulative 50% particle size (D50) of the pigment was measured at 25°C using a particle size distribution analyzer (NANOTRACWAVE, Microtrac Bell, Inc.). In the evaluation below, the evaluation of the non-aqueous ink composition was based on the larger change rate between "viscosity" and "volume-based cumulative 50% particle size (D50)" (indicated as "Storage Stability" in the table). Evaluation Criteria Evaluation 5: The rate of change in viscosity and the volume-based cumulative 50% particle size (D50) of the pigment are both less than 3%. Evaluation 4: The change rate of either viscosity or the volume-based cumulative 50% particle size (D50) of the pigment is between 3% and 5%. Evaluation 3: The change rate of either viscosity or the volume-based cumulative 50% particle size (D50) of the pigment is between 5% and 8%. Evaluation 2: The change rate of either viscosity or the volume-based cumulative 50% particle size (D50) of the pigment is between 8% and 10%. Evaluation 1: The change rate of either viscosity or the cumulative 50% particle size (D50) of the pigment by volume is 10% or more.

[0246] (Discharge stability) The ejection stability of the non-aqueous ink compositions in the examples, comparative examples, and reference examples was evaluated. Specifically, the non-aqueous ink compositions were filled into an inkjet printer (product name VersaArt RE-640, manufactured by Roland DG Corporation), and solid colors and fine lines were printed continuously on a recording medium (adhesive polyvinyl chloride film (IMAGin JT5829R: manufactured by MACtac)) in a bidirectional high-speed printing mode (360x720dpi) at a substrate surface temperature of 40°C. The presence or absence of dot defects, misaligned dots, and ink splatter was visually observed, and the number of occurrences was measured (indicated as "Ejection Stability" in the table). Evaluation Criteria Rating 5: Fine lines are reproduced correctly. Rating 4: Fine lines are generally reproduced correctly. Rating 3: There is a slight curvature in the thin lines. Rating 2: The point of impact was off, and a curve was visible. Rating 1: The point of impact is severely inaccurate, and it cannot reproduce thin lines.

[0247] (Intermittent discharge) The intermittent ejection properties of the non-aqueous ink compositions in the examples, comparative examples, and reference examples were evaluated. Specifically, using an inkjet printer (product name VersaArt RE-640, manufactured by Roland DG Corporation), intermittent printing was performed on a recording medium (adhesive polyvinyl chloride film (IMAGin JT5829R: manufactured by MACtac)) in a bidirectional high-speed printing mode (360x720dpi) over a long period at a substrate surface temperature of 40°C and at room temperature. The presence or absence of dot defects, misaligned dots, and ink splatter was observed, and the number of occurrences was counted for evaluation (indicated as "Intermittent ejection properties" in the table). Evaluation Criteria Rating 5: During the 24-hour test period, there were fewer than 10 instances of dead pixels, misaligned ink, or ink splatter. Rating 4: During the 24-hour test period, there were between 10 and 20 instances of dead pixels, misaligned ink, or ink splatter. Evaluation 3: During the 24-hour test period, there were between 20 and 30 instances of dead pixels, misaligned ink, or ink splatter. Evaluation 2: During the 24-hour test period, there were between 30 and 40 instances of dead pixels, misaligned ink, or ink splatter. Evaluation 1: During the 24-hour test period, there were 40 or more instances of dead pixels, misaligned ink, or ink splatter.

[0248] (Completely filled) The solid fill performance of the non-aqueous ink compositions in the examples, comparative examples, and reference examples was evaluated. Specifically, printing was performed on a recording medium (adhesive-backed polyvinyl chloride film (IMAGin JT5829R: MACtac)) using the above-mentioned inkjet printer (product name VersaArt RE-640, manufactured by Roland DG Corporation) in bidirectional high-speed printing mode (360x720dpi) at a substrate surface temperature of 40°C, and the solid fill (white areas) of the printed areas was confirmed (indicated as "solid fill" in the table). Rating 5: A uniform solid color is formed. Rating 4: While no white spots are visible to the naked eye, slight color unevenness is noticeable, but the design is not compromised. Rating 3: While no visible white spots are present, color unevenness is noticeable. Rating 2: White areas are visible. Evaluation 1: Significant white areas are visible, and a decrease in density is observed.

[0249] (Surface dryness) The surface drying properties of the non-aqueous ink compositions of the Examples, Comparative Examples, and Reference Examples were evaluated. Specifically, the non-aqueous ink compositions of the Examples and Comparative Examples were printed as solid images on a recording medium (adhesive-backed polyvinyl chloride film (IMAGin JT5829R: MACtac)) using an inkjet printer (product name VersaArt RE-640, manufactured by Roland DG Corporation) in high-quality print mode (1440x720dpi), and the time it took to dry at 40°C was measured (indicated as "Surface Drying Properties" in the table). Evaluation Criteria Rating 5: Dries in less than 2 minutes. Rating 4: Dries in between 2 and 4 minutes. Rating 3: Dries in 4 to 6 minutes. Rating 2: Dries in 6 to 8 minutes. Rating 1: Dries in over 8 minutes.

[0250] (Smudge-proof) The non-aqueous ink compositions of the examples, comparative examples, and reference examples were evaluated for their bleeding properties. Specifically, using the above-mentioned inkjet printer (product name VersaArt RE-640, manufactured by Roland DG Corporation), images with solid areas of each color containing 6pt characters of a different color were printed on a recording medium (adhesive polyvinyl chloride film (IMAGin JT5829R: manufactured by MACtac)) in high-quality printing mode (1440x720dpi) at a substrate surface temperature of 50°C. The resulting prints were dried in a 60°C oven for 5 minutes, and the bleeding of the prints was observed visually and with a magnifying glass (x10). Evaluation Criteria Rating 5: No ink bleeding was observed under magnification. Rating 4: No ink bleeding was observed to the naked eye, and the 6pt lettering is clear. Rating 3: Slight ink bleeding was observed visually, but the design was not compromised. Evaluation 2: Although some ink bleeding was observed visually, the 6pt characters were still legible. Evaluation 1: Significant ink bleeding was visible to the naked eye, making the 6pt text illegible.

[0251] (Color development) The color development properties of the non-aqueous ink compositions in the examples and comparative examples were evaluated. Specifically, a solid image was printed on a recording medium (adhesive polyvinyl chloride film (IMAGin JT5829R: MACtac)) using the above-mentioned inkjet printer (product name VersaArt RE-640, manufactured by Roland DG Corporation) in high-quality print mode (1440x720dpi). Saturation was determined by measurement using X-Rite eXact (manufactured by X-Rite Corporation) in accordance with JIS Z 8721, under the conditions of a viewing angle of 2°, a measurement range of 4mmφ, and a D65 light source. (Indicated as "Color Development" in the table). Evaluation Criteria Rating 5: Saturation is 100 or higher. Rating 4: Saturation is between 90 and 100. Rating 3: Saturation is between 80 and 90. Rating 2: Saturation is between 70 and 80. Rating 1: Saturation is below 70.

[0252] (weather resistance) The weather resistance of printed materials prepared using the non-aqueous ink compositions of the Examples, Comparative Examples, and Reference Examples was evaluated. The non-aqueous ink compositions of the Examples and Comparative Examples were used to print solid images on a recording medium (adhesive polyvinyl chloride film (IMAGin JT5829R: MACtac)) using an inkjet method with an inkjet printer (product name VersaArt RE-640, manufactured by Roland DG Corporation) in high-quality print mode (1440x720dpi), and dried at 40°C for 1 hour. The obtained data was placed inside a xenon weather meter (ATLAS Ci4000: manufactured by Toyo Seiki) and a cycle test was performed. The test conditions were based on JIS K-5600-7-7, with a black panel temperature of 63°C and a xenon lamp irradiance of 60 W / m². 2 The temperature inside the test layer was maintained at 38°C. Segment 1 was irradiated with water for 102 minutes while maintaining a humidity of 50%, and Segment 2 was irradiated with water for 18 minutes. This constituted one cycle. 50 cycles constituted one set, and this cycle test was continued for 10 sets. The value of the hue change ΔE before and after the test was evaluated. Hue was evaluated under the following conditions: Using X-Rite eXact (manufactured by X-Rite), with a viewing angle of 2°, a measurement range of 4 mmφ, and a D65 light source, L* and a * , b * The value was measured (labeled "Weather Resistance" in the table). Hue change ΔE is L before the test. *1 a *1 , b *1 , after the exam L *2 a *2 , b *2 Using the value of , it can be calculated using the following formula. ΔE=((L *1 -L *2 ) 2+(a *1 -a *2 ) 2 +(b *1 -b *2 ) 2 ) (1 / 2) Evaluation Criteria Rating 5: ΔE is less than 10.0. Evaluation 4: ΔE is less than 20.0 and greater than or equal to 10.0. Evaluation 3: ΔE is less than 30.0 or greater than 20.0. Evaluation 2: ΔE is less than 40.0 or greater than 30.0. Evaluation 1: ΔE is 50.0 or higher.

[0253] (Glossiness) The glossiness of the non-aqueous ink compositions of the Examples, Comparative Examples, and Reference Examples was evaluated. Specifically, the non-aqueous ink compositions of the Examples and Comparative Examples were printed on a recording medium (adhesive polyvinyl chloride film (IMAGin JT5829R: MACtac)) using an inkjet method with an inkjet printer (product name VersaArt RE-640, manufactured by Roland DG Corporation) in high-quality printing mode (1440x720dpi) at a substrate surface temperature of 40°C. After drying in a 60°C oven for 5 minutes, the 20° glossiness of the printed material was measured. The glossiness was measured using a handheld gloss meter PhopointIQ-S (manufactured by Konica Minolta Corporation) (indicated as "Glossiness" in the table). Evaluation Criteria Rating 5: 20° Glossiness 70 or higher Rating 4: 20° Gloss score between 65 and 70 Rating 3: 20° Glossiness between 55 and 65 Rating 2: 20° Gloss is between 50 and 55 Rating 1: Gloss level less than 50 (20°)

[0254] (Color stability (sedimentation)) The sedimentation properties of the non-aqueous ink compositions in the examples, comparative examples, and reference examples were evaluated. Specifically, 30 g of the non-aqueous ink composition was stored at room temperature for one month, and 1 g of the supernatant ink after the test was taken and spread onto a recording medium (adhesive polyvinyl chloride film (IMAGin JT5829R: MACtac)) using a bar coater #8 and dried in a 40°C oven. The value of the hue change ΔE before and after the test was evaluated. The hue was evaluated under the following conditions: Using an X-Rite eXact (X-Rite Corporation), with a viewing angle of 2°, a measurement range of 4 mmφ, and a D65 light source, L * a * , b * The values ​​were measured (indicated as "Color Stability (Settling)" in the table). Hue change ΔE is L before the test. *1 a *1 , b *1 , after the exam L *2 a *2 , b *2 Using the value of , it can be calculated using the following formula. ΔE=((L *1 -L *2 ) 2 +(a *1 -a *2 ) 2 +(b *1 -b *2 ) 2 ) (1 / 2) Evaluation Criteria Rating 5: ΔE is less than 2.0. Evaluation 4: ΔE is less than 2.5 or greater than 2.0. Evaluation 3: ΔE is less than 3.0 and greater than or equal to 2.5. Evaluation 2: ΔE is less than 3.5 or greater than 3.0. Evaluation 1: ΔE is 3.5 or higher.

[0255] [Table 3]

[0256] [Table 4]

[0257] [Table 5]

[0258] [Table 6]

[0259] [Table 7]

[0260] [Table 8]

[0261] [Table 9]

[0262] [Table 10]

[0263] As can be seen from Tables 3 to 10, the non-aqueous ink compositions of the examples, which contain pigment A1 represented by formula (1-1) and whose pH is in the range of 3 to 9, exhibit good various properties required for non-aqueous ink compositions ejected by an inkjet method.

[0264] In particular, among the non-aqueous ink compositions of Examples 1-10 to 1-13 in which the pH of pigment A1 was changed, the non-aqueous ink compositions of Examples 1-10 to 1-12, in which the pH of pigment A1 was in the range of 4 to 8, showed better storage stability compared to Example 1-13.

[0265] Furthermore, in the non-aqueous ink compositions of Examples 1-14 to 1-30 and 1-72 to 1-75, in which the content of resin with an intrinsic viscosity of 90 mL / g or more at 25°C was changed, the non-aqueous ink compositions of the examples in which the resin with an intrinsic viscosity of 90 mL / g or more at 25°C was in the range of 5% by mass or less of the total resin amount showed improved solid filling and intermittent ejection compared to the non-aqueous ink compositions of the examples in which it was in the range of more than 5% by mass.

[0266] Furthermore, the non-aqueous ink composition of Example 1-1, which contains organic solvent B (at least one selected from the group consisting of alkylamide solvents (b1), cyclic amide solvents (b2), and lactone solvents (b3)), exhibited better various properties required for non-aqueous ink compositions ejected by inkjet methods compared to the non-aqueous ink compositions of Examples 1-31 to 1-33, which do not contain organic solvent B.

[0267] Furthermore, in Examples 1-34 to 1-41, in which the content of organic solvent B was changed, the non-aqueous ink compositions of Examples 1-34 to 1-40, in which the content of organic solvent B was in the range of 1% by mass to 90% by mass, exhibited better color development and weather resistance compared to the non-aqueous ink composition of Example 1-41, and had better various properties required for non-aqueous ink compositions ejected by the inkjet method.

[0268] Furthermore, in Examples 1-42 to 1-51, 1-74, and 1-75, in which the type of organic solvent B (alkylamide solvent (b1), cyclic amide solvent (b2), and lactone solvent (b3)) was changed, various properties required for non-aqueous ink compositions ejected by the inkjet method were similarly improved. In fact, non-aqueous ink compositions containing organic solvent B (at least one selected from the group consisting of alkylamide solvent (b1), cyclic amide solvent (b2), and lactone solvent (b3)) demonstrated the effects of the present invention particularly effectively.

[0269] Furthermore, in Examples 1-52 to 1-55, in which the pigment A1 content was changed, the non-aqueous ink compositions of Examples 1-52 to 1-54, in which the pigment A1 content was 0.1% by mass or more and 8.0% by mass or less of the total amount of the non-aqueous ink composition, showed better storage stability compared to Example 1-55, and it was found that they exhibited better various properties required for non-aqueous ink compositions ejected by the inkjet method.

[0270] Furthermore, in Examples 1-56 to 1-59, in which the volume-based cumulative 90% particle size (D90) of pigment A1 was changed, a tendency was observed where the smaller the volume-based cumulative 90% particle size (D90), the better the dispensing stability.

[0271] Furthermore, in Examples 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, which used a pigment dispersant having a basic group, showed improved discharge stability compared to the non-aqueous ink composition of Example 60. Among these, the non-aqueous ink compositions of Examples 1-62 to 1-64, which had an amine value in the range of 20 mg KOH / g to 100 mg KOH / g, showed particularly improved discharge stability.

[0272] Furthermore, in Examples 1-66 to 1-69, in which the pigment dispersant content was changed, the ink compositions of Examples 1-66 to 1-68, in which the pigment dispersant content was in the range of 5 parts by mass to 150 parts by mass per 100 parts by mass of pigment in the non-aqueous ink composition, showed improved color development and surface drying properties compared to the non-aqueous ink composition of Example 1-69.

[0273] Furthermore, the ink compositions of Examples 1-70 and 1-71, which did not contain surfactants having a siloxane skeleton, exhibited reduced gloss compared to the ink composition of Example 1-1.

[0274] On the other hand, the non-aqueous ink composition of Comparative Example 1-1, which contains pigment A1 with a pH of less than 3, exhibits reduced storage stability and solid filling ability, and does not meet the various properties required for non-aqueous ink compositions ejected by inkjet methods. Furthermore, the non-aqueous ink composition of Comparative Example 1-2, which contains pigment A1 with a pH greater than 9, exhibits reduced storage stability and ejection stability, and does not meet the various properties required for non-aqueous ink compositions ejected by inkjet methods.

[0275] Furthermore, Reference Examples 1-1 and 1-2, which do not contain pigment A1 represented by formula (1-1) but contain CI pigment orange 31 and CI pigment 64, satisfy the characteristics required for non-aqueous ink compositions ejected by the inkjet method. This confirms that the tendency to aggregate in non-aqueous ink compositions is a unique challenge for non-aqueous ink compositions containing perinone-based pigments.

[0276] (Second Embodiment) 1. Preparation of resin (1) Acrylic resin To 300 g of diethylene glycol diethyl ether maintained at 100°C, a mixture of 150 g of methyl methacrylate, 50 g of butyl methacrylate, and a predetermined amount of t-butyl peroxy-2-ethylhexanoate (polymerization initiator) was added dropwise over 1.5 hours. After the addition was complete, the mixture was reacted at 100°C for 2 hours and then cooled to obtain a colorless, transparent polymer solution of methyl methacrylate. Subsequently, the solvent was thoroughly removed from this polymer solution to obtain the polymer of methyl methacrylate. At this time, the amount of t-butyl peroxy-2-ethylhexanoate, the polymerization initiator, was changed to control the average polymerization molecular weight of methyl methacrylate (acrylic resin) to 30,000 to 105,000 (the mass of the polymerization initiator used at this time is listed in Table 11 below. In Table 11, it is labeled as "Amount of Initiator").

[0277] (2) Vinyl chloride-vinyl acetate copolymer resin In an autoclave equipped with a stirring device, after purging with nitrogen, 100 parts deionized water, 40 parts methanol, 32 parts vinyl chloride, 5 parts vinyl acetate, 0.2 parts glycidyl methacrylate, 3.55 parts hydroxypropyl acrylate, 0.1 part hydroxypropyl methylcellulose (suspending agent), 0.026 parts di-2-ethylhexyl peroxydicarbonate (polymerization initiator), and a predetermined amount of di-3,5,5-trimethylhexanol peroxide (polymerization initiator) were charged. The mixture was heated to 63°C while stirring under a nitrogen gas atmosphere. Immediately after reaching 63°C, 48 parts vinyl chloride was continuously injected over 6 hours, and a mixture of 0.6 parts glycidyl methacrylate and 10.65 parts hydroxypropyl acrylate was continuously injected over 5.4 hours to induce a copolymerization reaction. When the internal pressure of the autoclave reached 0.3 MPa, the remaining pressure was released, the mixture was cooled, and the resin slurry was extracted, filtered, and dried to obtain a vinyl chloride copolymer resin. At this time, the amount of di-3,5,5-trimethylhexanol peroxide, which is the polymerization initiator, was changed to control the average polymerization molecular weight of the vinyl chloride-vinyl acetate copolymer resin to be between 40,000 and 75,000 (the mass of the polymerization initiator used at this time is listed in Table 11 below. In Table 11, it is labeled as "Amount of Initiator").

[0278] (3) Cellulose resins Commercially available cellulose-based resins (CAB551-0.01 and CAB553-0.4 from Eastman Chemical) were used.

[0279] (4) Polyester 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 parts by mass of tetrabutyl titanate were placed in a round-bottom flask, and the temperature was gradually raised to 240°C over 4 hours while removing the distillate from the system to carry out the esterification reaction. After the completion of the esterification reaction, the pressure was reduced to 10 mmHg over 30 minutes, and the temperature was raised to 250°C to carry out initial polymerization. Subsequently, late polymerization was carried out at a pressure of 1 mmHg or less for 1 hour to obtain a polyester resin.

[0280] (5) Polyurethane resin 192.5 parts by mass of polycarbonate diol (Praxel CD-220: manufactured by Daicel), 41.6 parts by mass of isophorone diisocyanate (IPDI: manufactured by Evonik), and 100 parts by mass of N,N-diethylformamide (DEF) were placed in a round-bottom flask and mixed uniformly. Then, a mixture of 0.01 parts of T100BHJ (catalyst) and 0.09 parts of N,N-diethylformamide (DEF) was added and reacted at 75°C for 3 hours to obtain a prepolymer having isocyanate groups at the ends. 250 parts by mass of N,N-diethylformamide (DEF) were added to this and dissolved uniformly. Then, a chain extension solution prepared by dissolving 12 parts by mass of 3-aminomethyl3,5,5-trimethylcyclohexylamine (IPD: manufactured by Evonik) in 100 parts by mass of N,N-diethylformamide (DEF) was added and the mixture was stirred at 60°C for a further 40 minutes. Subsequently, a reaction stopper was added, consisting of 3.8 parts of monoisopropanolamine (MIPA: manufactured by Daicel) dissolved in 50 parts by mass of N,N-diethylformamide (DEF). Finally, 250 parts by mass of N,N-diethylformamide (DEF) were added to obtain a polyurethane solution with a solid content of 25.0% by mass.

[0281] 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 percentage of resins with an intrinsic viscosity of 90 mL / g or higher at 25°C. The weight-average molecular weight (relative molecular mass) was measured by GPC (gel permeation chromatography). The percentage of resins with an intrinsic viscosity of 90 mL / g or higher was determined by connecting a viscometer (WYATT ViscoStar III) and a refractive index detector (WYATT Optilab T-rEX) to a Shimadzu SEC(GPC) system, using tetrahydrofuran as the developing solvent. First, the sample was passed through a column heated to 40°C in the Shimadzu SEC(GPC) system, and then the pass-through was cooled to 25°C. The specific viscosity [η] was measured using the viscometer. SP [η] is determined, and the concentration C is determined using a refractive index detector. Lim([η] SP In the formula ] / C), the intrinsic viscosity was determined by extrapolating the concentration C to 0.

[0282] [Table 11]

[0283] 2. Synthesis of Pigment A2 Synthesized pigments A2 1-3 were prepared according to the conditions described in Table 12. Specifically, 2 parts by mass of the diketopyrrolopyrrole pigment (a8) in Table 12 were dispersed in the solvent (a9) in Table 12, and (a10) in part (a11) of the solvent (a10) in Table 12 was added. After stirring for (a13) hours at the temperature conditions (a12) in Table 12, the mixture was washed with water to obtain synthetic pigments A2 1, 2, and 3.

[0284] [Table 12] (In the table, "none" in (a10) and (a11) means that no substituent agent was added.)

[0285] 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 (Table 12 (a14)).

[0286] 3. Preparation of non-aqueous ink composition Non-aqueous ink compositions for the examples and comparative examples were prepared with each component in the proportions shown in the table below, according to the respective organic solvents, resins, dispersants, and pigments (colorants). Specifically, the non-aqueous ink compositions were prepared by dispersing each component with zirconia beads using a paint shaker. The unit is mass%. The particle size of the zirconia beads and the dispersion time are listed in Tables 13 to 20 below.

[0287] Furthermore, the volume-based cumulative 90% particle size (D90) of the pigments contained in the non-aqueous ink composition was measured using a particle size distribution analyzer (NANOTRACWAVE particle size analyzer manufactured by Microtrac Bell Co., Ltd.).

[0288] 4. Rating 1 (Storage stability) The storage stability of the non-aqueous ink compositions of the examples, comparative examples, and reference examples was evaluated. Specifically, the non-aqueous ink compositions were stored at 60°C for one month, and the changes in viscosity and the volume-based cumulative 50% particle size (D50) of the pigment before and after the test were observed. The storage stability was evaluated according to the following criteria. The viscosity of the ink was measured at 20°C using a falling-ball viscometer (AMVn, Anton Paar), and the volume-based cumulative 50% particle size (D50) of the pigment was measured at 25°C using a particle size distribution analyzer (NANOTRACWAVE, Microtrac Bell, Inc.). In the evaluation below, the evaluation of the non-aqueous ink composition was based on the larger change rate between "viscosity" and "volume-based cumulative 50% particle size (D50)" (indicated as "Storage Stability" in the table). Evaluation Criteria Evaluation 5: The rate of change in viscosity and the volume-based cumulative 50% particle size (D50) of the pigment are both less than 3%. Evaluation 4: The change rate of either viscosity or the volume-based cumulative 50% particle size (D50) of the pigment is between 3% and 5%. Evaluation 3: The change rate of either viscosity or the volume-based cumulative 50% particle size (D50) of the pigment is between 5% and 8%. Evaluation 2: The change rate of either viscosity or the volume-based cumulative 50% particle size (D50) of the pigment is between 8% and 10%. Evaluation 1: The change rate of either viscosity or the cumulative 50% particle size (D50) of the pigment by volume is 10% or more.

[0289] (Discharge stability) The ejection stability of the non-aqueous ink compositions in the examples, comparative examples, and reference examples was evaluated. Specifically, the non-aqueous ink compositions were filled into an inkjet printer (product name VersaArt RE-640, manufactured by Roland DG Corporation), and solid colors and fine lines were printed continuously on a recording medium (adhesive polyvinyl chloride film (IMAGin JT5829R: manufactured by MACtac)) in a bidirectional high-speed printing mode (360x720dpi) at a substrate surface temperature of 40°C. The presence or absence of dot defects, misaligned dots, and ink splatter was visually observed, and the number of occurrences was measured (indicated as "Ejection Stability" in the table). Evaluation Criteria Rating 5: Fine lines are reproduced correctly. Rating 4: Fine lines are generally reproduced correctly. Rating 3: There is a slight curvature in the thin lines. Rating 2: The point of impact was off, and a curve was visible. Rating 1: The point of impact is severely inaccurate, and it cannot reproduce thin lines.

[0290] (Intermittent discharge) The intermittent ejection properties of the non-aqueous ink compositions in the examples, comparative examples, and reference examples were evaluated. Specifically, using an inkjet printer (product name VersaArt RE-640, manufactured by Roland DG Corporation), intermittent printing was performed on a recording medium (adhesive polyvinyl chloride film (IMAGin JT5829R: manufactured by MACtac)) in a bidirectional high-speed printing mode (360x720dpi) over a long period at a substrate surface temperature of 40°C and at room temperature. The presence or absence of dot defects, misaligned dots, and ink splatter was observed, and the number of occurrences was counted for evaluation (indicated as "Intermittent ejection properties" in the table). Evaluation Criteria Rating 5: During the 24-hour test period, there were fewer than 10 instances of dead pixels, misaligned ink, or ink splatter. Rating 4: During the 24-hour test period, there were between 10 and 20 instances of dead pixels, misaligned ink, or ink splatter. Evaluation 3: During the 24-hour test period, there were between 20 and 30 instances of dead pixels, misaligned ink, or ink splatter. Evaluation 2: During the 24-hour test period, there were between 30 and 40 instances of dead pixels, misaligned ink, or ink splatter. Evaluation 1: During the 24-hour test period, there were 40 or more instances of dead pixels, misaligned ink, or ink splatter.

[0291] (Completely filled) The solid fill performance of the non-aqueous ink compositions in the examples, comparative examples, and reference examples was evaluated. Specifically, printing was performed on a recording medium (adhesive-backed polyvinyl chloride film (IMAGin JT5829R: MACtac)) using the above-mentioned inkjet printer (product name VersaArt RE-640, manufactured by Roland DG Corporation) in bidirectional high-speed printing mode (360x720dpi) at a substrate surface temperature of 40°C, and the solid fill (white areas) of the printed areas was confirmed (indicated as "solid fill" in the table). Evaluation Criteria Rating 5: A uniform solid color is formed. Rating 4: While no white spots are visible to the naked eye, slight color unevenness is noticeable, but the design is not compromised. Rating 3: While no visible white spots are present, color unevenness is noticeable. Rating 2: White areas are visible. Evaluation 1: Significant white areas are visible, and a decrease in density is observed.

[0292] (Surface dryness) The surface drying properties of the non-aqueous ink compositions of the Examples, Comparative Examples, and Reference Examples were evaluated. Specifically, the non-aqueous ink compositions of the Examples and Comparative Examples were printed as solid images on a recording medium (adhesive-backed polyvinyl chloride film (IMAGin JT5829R: MACtac)) using an inkjet printer (product name VersaArt RE-640, manufactured by Roland DG Corporation) in high-quality print mode (1440x720dpi), and the time it took to dry at 40°C was measured (indicated as "Surface Drying Properties" in the table). Evaluation Criteria Rating 5: Dries in less than 2 minutes. Rating 4: Dries in between 2 and 4 minutes. Rating 3: Dries in 4 to 6 minutes. Rating 2: Dries in 6 to 8 minutes. Rating 1: Dries in over 8 minutes.

[0293] (Smudge-proof) The non-aqueous ink compositions of the examples, comparative examples, and reference examples were evaluated for their bleeding properties. Specifically, using the above-mentioned inkjet printer (product name VersaArt RE-640, manufactured by Roland DG Corporation), images with solid areas of each color containing 6pt characters of a different color were printed on a recording medium (adhesive polyvinyl chloride film (IMAGin JT5829R: manufactured by MACtac)) in high-quality printing mode (1440x720dpi) at a substrate surface temperature of 50°C. The resulting prints were dried in a 60°C oven for 5 minutes, and the bleeding of the prints was observed visually and with a magnifying glass (x10). Evaluation Criteria Rating 5: No ink bleeding was observed under magnification. Rating 4: No ink bleeding was observed to the naked eye, and the 6pt lettering is clear. Rating 3: Slight ink bleeding was observed visually, but the design was not compromised. Evaluation 2: Although some ink bleeding was observed visually, the 6pt characters were still legible. Evaluation 1: Significant ink bleeding was visible to the naked eye, making the 6pt text illegible.

[0294] (Coating film abrasion resistance) The abrasion resistance of the non-aqueous ink compositions of the Examples, Comparative Examples, and Reference Examples was evaluated. Specifically, the non-aqueous ink compositions of the Examples and Comparative Examples were printed as solid images on a recording medium (adhesive-backed polyvinyl chloride film (IMAGin JT5829R: MACtac)) using an inkjet printer (product name VersaArt RE-640, manufactured by Roland DG Corporation) in high-quality printing mode (1440x720dpi), and dried at 40°C. The printed surface of the printed material was rubbed with a test cloth under a load of 200g for 50 back-and-forth strokes, and the abrasion resistance was evaluated visually. (Indicated as "Abrasion Resistance" in the table.) Evaluation Criteria Rating 5: The ink film did not peel off, and no ink adhered to the test cloth. Rating 4: The ink film did not peel off, but there was ink residue on the test cloth. Evaluation 3: The ink film peeled off slightly, and some of the ink film adhered to the test cloth. Evaluation 2: The ink film peeled off slightly, and some of the ink film adhered to the test cloth. Evaluation 1: Most of the ink film peeled off, and the ink film adhered to the test cloth.

[0295] (Cleaning recovery) For the non-aqueous ink compositions of the Examples, Comparative Examples, and Reference Examples, we evaluated whether nozzle clogging in the print head could be resolved by the printer's cleaning operation. Specifically, using the above-mentioned inkjet printer equipped with a cleaning system (product name VersaArt RE-640, manufactured by Roland DG Corporation), the ink compositions of the Examples and Comparative Examples were filled and printed in high-quality print mode (1440x720dpi) at 1.80m². 2 A solid image was printed, left at room temperature (25°C) for one week, then a nozzle check pattern was printed, and cleaning was performed until there were no more gaps (indicated as "Cleaning Recovery" in the table). Evaluation Criteria Rating 5: No omissions. Rating 4: Nozzle clogging is cleared with just one normal cleaning. Rating 3: Nozzle clogging can be cleared with 2-3 normal cleaning cycles. Rating 2: Nozzle clogging can be cleared with 4-5 normal cleaning cycles. Rating 1: Even after 6 normal cleaning cycles, the nozzle clog was not cleared.

[0296] (weather resistance) The weather resistance of printed materials prepared using the non-aqueous ink compositions of the Examples, Comparative Examples, and Reference Examples was evaluated. The non-aqueous ink compositions of the Examples and Comparative Examples were used to print solid images on a recording medium (adhesive polyvinyl chloride film (IMAGin JT5829R: MACtac)) using an inkjet method with an inkjet printer (product name VersaArt RE-640, manufactured by Roland DG Corporation) in high-quality print mode (1440x720dpi), and dried at 40°C for 1 hour. The obtained recording was put into a xenon weather meter (ATLAS Ci4000: manufactured by Toyo Seiki), and a cycle test was conducted. The test conditions were based on JIS K―5600-7-7, with a black panel temperature of 63°C, a xenon lamp irradiance of 60 W / m 2 , the temperature inside the test layer was maintained at 38°C. In segment 1, the humidity was maintained at 50% for 102 minutes, and in segment 2, water irradiation was carried out for 18 minutes. This was defined as one cycle. A set consisted of 50 cycles, and this cycle test was continuously carried out for 10 sets. The value of the hue change ΔE before and after the test was evaluated. The hue was evaluated under the following conditions. Using X-Rite eXact (manufactured by X-Rite), the values of L*, a*, and b* were measured under the conditions of a viewing angle of 2°, a measurement range of 4 mmφ, and a D65 light source (indicated as "weather resistance" in the table). The hue change ΔE was calculated using the values of L *1 , a *1 , b *1 )]], L *2 , a *2 , b *2 before and after the test, and was obtained by the following formula ΔE = ((L *1 - L *2 ) 2 + (a *1 - a *2 ) 2 + (b *1 - b *2 ) 2 ) (1 / 2) Evaluation Criteria Evaluation 5: ΔE is less than 10.0. Evaluation 4: ΔE is less than 20.0 and greater than or equal to 10.0. Evaluation 3: ΔE is less than 30.0 and greater than or equal to 20.0. Evaluation 2: ΔE is less than 40.0 and greater than or equal to 30.0. Evaluation 1: ΔE is greater than or equal to 50.0.

[0297]

Table 13

[0298] [Table 14]

[0299] [Table 15]

[0300] [Table 16]

[0301] [Table 17]

[0302] [Table 18]

[0303] [Table 19]

[0304] [Table 20]

[0305] As can be seen from Tables 13 to 20, if the non-aqueous ink composition of the example contains pigment A2 represented by formula (1-2) and the pH of pigment A2 is in the range of 3 to 9, then even if a pigment containing diketopyrrolopyrrole pigment is used as the pigment, it will have high storage stability and high cleaning recovery properties.

[0306] In particular, among the non-aqueous ink compositions of Examples 2-9 to 2-12 in which the pH of pigment A2 was changed, the non-aqueous ink compositions of Examples 2-10 to 2-11, in which the pH of pigment A2 was in the range of 6 to 8, showed better storage stability compared to Examples 9 and 12.

[0307] Furthermore, in the non-aqueous ink compositions of Examples 2-14 to 2-29, in which the content of resin with an intrinsic viscosity of 90 mL / g or more at 25°C was changed, the non-aqueous ink compositions of the examples in which the resin with an intrinsic viscosity of 90 mL / g or more at 25°C was in the range of 5% by mass or less of the total resin amount showed improved solid filling and intermittent ejection compared to the non-aqueous ink compositions of the examples in which it was in the range of more than 5% by mass.

[0308] Furthermore, the non-aqueous ink composition of Example 2-1, which contains organic solvent B (at least one selected from the group consisting of alkylamide solvents (b1), cyclic amide solvents (b2), and lactone solvents (b3)), exhibits superior storage stability and cleaning recovery compared to the non-aqueous ink compositions of Examples 2-30 to 2-32, which do not contain organic solvent B, demonstrating particularly effective performance of the effects of the present invention.

[0309] Furthermore, in Examples 2-33 to 2-40, in which the content of organic solvent B was changed, it was found that the non-aqueous ink compositions of Examples 2-33 to 2-39, in which the content of organic solvent B was in the range of 1% by mass to 90% by mass, had higher storage stability and cleaning recovery properties compared to the non-aqueous ink composition of Example 2-40, and thus particularly effectively demonstrated the effects of the present invention.

[0310] Furthermore, in Examples 2-41 to 2-50, 2-71, and 2-72, in which the type of organic solvent B was changed to alkylamide solvent (b1), cyclic amide solvent (b2), and lactone solvent (b3), the various properties required for non-aqueous ink compositions ejected by the inkjet method were similarly improved. This indicates that non-aqueous ink compositions containing organic solvent B (at least one selected from the group consisting of alkylamide solvent (b1), cyclic amide solvent (b2), and lactone solvent (b3)) are particularly effective in achieving the effects of the present invention.

[0311] Furthermore, in Examples 2-51 to 2-54, in which the pigment A2 content was changed, the non-aqueous ink compositions of Examples 2-51 to 2-53, in which the pigment A2 content was 0.1% by mass or more and 8.0% by mass or less of the total amount of the non-aqueous ink composition, showed better storage stability compared to Example 2-54.

[0312] Furthermore, in Examples 2-55 to 2-57, in which the volume-based cumulative 90% particle size (D90) of pigment A2 was changed, a tendency was observed where the smaller the volume-based cumulative 90% particle size (D90), the better the storage stability and dispensing stability.

[0313] Furthermore, in Examples 2-59 to 2-64 and 2-70, in which the type of pigment dispersant was changed, the non-aqueous ink compositions of Examples 2-60 to 2-64 and 2-70, which used a pigment dispersant having a basic group, showed improved discharge stability compared to the non-aqueous ink composition of Example 2-60. Among these, the non-aqueous ink compositions of Examples 2-60 to 2-63, in which the amine value was in the range of 20 mg KOH / g to 100 mg KOH / g, showed particularly improved discharge stability.

[0314] Furthermore, in Examples 2-65 to 2-68, in which the pigment dispersant content was changed, the ink compositions of Examples 2-65 to 2-67, in which the pigment dispersant content was in the range of 5 parts by mass to 150 parts by mass per 100 parts by mass of pigment in the non-aqueous ink composition, showed improved surface drying properties and coating film abrasion resistance compared to the ink composition of Example 2-68.

[0315] Furthermore, the ink compositions of Examples 2-69, which did not contain surfactants having a siloxane skeleton, showed a relatively slight decrease in coating film abrasion resistance.

[0316] On the other hand, the ink compositions of Comparative Examples 2-1 and 2-2, which contain pigment A2 and have a pH outside the range of 3 to 9, do not exhibit the effects of the present invention.

[0317] Furthermore, Reference Examples 2-1 and 2-2, which do not contain pigment A2 (diketopyrrolopyrrole pigment) represented by formula (1-2) but contain CI pigment red 149 and CI pigment red 188, satisfy the characteristics required for non-aqueous ink compositions ejected by the inkjet method. This confirms that the tendency to aggregate in non-aqueous ink compositions is a unique problem for non-aqueous ink compositions containing diketopyrrolopyrrole pigments.

[0318] (Third embodiment) 1. Preparation of resin (1) Acrylic resin To 300 g of diethylene glycol diethyl ether maintained at 100°C, a mixture of 150 g of methyl methacrylate, 50 g of butyl methacrylate, and a predetermined amount of t-butyl peroxy-2-ethylhexanoate (polymerization initiator) was added dropwise over 1.5 hours. After the addition was complete, the mixture was reacted at 100°C for 2 hours and then cooled to obtain a colorless, transparent polymer solution of methyl methacrylate. Subsequently, the solvent was thoroughly removed from this polymer solution to obtain the polymer of methyl methacrylate. At this time, the amount of t-butyl peroxy-2-ethylhexanoate, the polymerization initiator, was changed to control the average polymerization molecular weight of methyl methacrylate (acrylic resin) to 30,000 to 105,000 (the mass of the polymerization initiator used at this time is listed in Table 1 below. In Table 21, it is indicated as "Amount of Initiator").

[0319] (2) Vinyl chloride-vinyl acetate copolymer resin In an autoclave equipped with a stirring device, after purging with nitrogen, 100 parts deionized water, 40 parts methanol, 32 parts vinyl chloride, 5 parts vinyl acetate, 0.2 parts glycidyl methacrylate, 3.55 parts hydroxypropyl acrylate, 0.1 part hydroxypropyl methylcellulose (suspending agent), 0.026 parts di-2-ethylhexyl peroxydicarbonate (polymerization initiator), and a predetermined amount of di-3,5,5-trimethylhexanol peroxide (polymerization initiator) were charged. The mixture was heated to 63°C while stirring under a nitrogen gas atmosphere. Immediately after reaching 63°C, 48 parts vinyl chloride was continuously injected over 6 hours, and a mixture of 0.6 parts glycidyl methacrylate and 10.65 parts hydroxypropyl acrylate was continuously injected over 5.4 hours to induce a copolymerization reaction. When the internal pressure of the autoclave reached 0.3 MPa, the remaining pressure was released, the mixture was cooled, and the resin slurry was extracted, filtered, and dried to obtain a vinyl chloride copolymer resin. At this time, the amount of di-3,5,5-trimethylhexanol peroxide, which is the polymerization initiator, was changed to control the average polymerization molecular weight of the vinyl chloride-vinyl acetate copolymer resin to be between 40,000 and 75,000 (the mass of the polymerization initiator used at this time is listed in Table 21 below. In Table 21, it is labeled as "Amount of Initiator").

[0320] (3) Cellulose resins Commercially available cellulose-based resins (CAB551-0.01 and CAB553-0.4 from Eastman Chemical) were used.

[0321] (4) Polyester 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 parts by mass of tetrabutyl titanate were placed in a round-bottom flask, and the temperature was gradually raised to 240°C over 4 hours while removing the distillate from the system to carry out the esterification reaction. After the completion of the esterification reaction, the pressure was reduced to 10 mmHg over 30 minutes, and the temperature was raised to 250°C to carry out initial polymerization. Subsequently, late polymerization was carried out at a pressure of 1 mmHg or less for 1 hour to obtain a polyester resin.

[0322] (5) Polyurethane resin 192.5 parts by mass of polycarbonate diol (Praxel CD-220: manufactured by Daicel), 41.6 parts by mass of isophorone diisocyanate (IPDI: manufactured by Evonik), and 100 parts by mass of N,N-diethylformamide (DEF) were placed in a round-bottom flask and mixed uniformly. Then, a mixture of 0.01 parts by mass of T100BHJ (catalyst) and 0.09 parts by mass of N,N-diethylformamide (DEF) was added and reacted at 75°C for 3 hours to obtain a prepolymer having isocyanate groups at the ends. 250 parts by mass of N,N-diethylformamide (DEF) were added and uniformly dissolved. Then, a chain extension solution prepared by dissolving 12 parts by mass of 3-aminomethyl3,5,5-trimethylcyclohexylamine (IPD: manufactured by Evonik) in 100 parts by mass of DEF was added and the mixture was stirred at 60°C for a further 40 minutes. Subsequently, a reaction stopper was added, consisting of 3.8 parts by mass of monoisopropanolamine (MIPA: manufactured by Daicel) dissolved in 50 parts by mass of N,N-diethylformamide (DEF). Finally, 250 parts by mass of N,N-diethylformamide (DEF) were added to obtain a polyurethane solution with a solid content of 25.0% by mass.

[0323] 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 percentage of resins with an intrinsic viscosity of 90 mL / g or higher at 25°C. The weight-average molecular weight (relative molecular mass) was measured by GPC (gel permeation chromatography). The percentage of resins with an intrinsic viscosity of 90 mL / g or higher was determined by connecting a viscometer (WYATT ViscoStar III) and a refractive index detector (WYATT Optilab T-rEX) to a Shimadzu SEC(GPC) system, using tetrahydrofuran as the developing solvent. First, the sample was passed through a column heated to 40°C in the Shimadzu SEC(GPC) system, and then the pass-through was cooled to 25°C. The specific viscosity [η] was measured using the viscometer. SP [η] is determined, and the concentration C is determined using a refractive index detector. Lim([η] SP In the formula ] / C), the intrinsic viscosity was determined by extrapolating the concentration C to 0.

[0324] [Table 21]

[0325] 2. Preparation of non-aqueous ink composition Non-aqueous ink compositions for the examples and comparative examples were prepared with each component in the proportions shown in the table below, according to the respective organic solvents, resins, dispersants, and pigments (colorants). Specifically, the non-aqueous ink compositions were prepared by dispersing each component with zirconia beads using a paint shaker. The unit is mass%. The particle size of the zirconia beads and the dispersion time are listed in Tables 22-29 below.

[0326] Furthermore, the volume-based cumulative 90% particle size (D90) of the pigments contained in the non-aqueous ink composition was measured using a particle size distribution analyzer (NANOTRACWAVE particle size analyzer manufactured by Microtrac Bell Co., Ltd.).

[0327] 3. Rating 1 (Storage stability) The storage stability of the non-aqueous ink compositions of the Examples, Comparative Examples, and Reference Examples was evaluated. Specifically, the non-aqueous ink compositions were stored at 60°C for one month, and the changes in viscosity and the volume-based cumulative 50% particle size (D50) of the pigment before and after the test were observed. The storage stability was evaluated according to the following criteria. The viscosity of the ink was measured at 20°C using a falling-ball viscometer (AMVn, Anton Paar), and the volume-based cumulative 50% particle size (D50) of the pigment was measured at 25°C using a particle size distribution analyzer (NANOTRACWAVE, Microtrac Bell, Inc.). In the evaluation below, the evaluation of the non-aqueous ink composition was based on the larger change rate between "viscosity" and "volume-based cumulative 50% particle size (D50) of the pigment" (indicated as "Storage Stability" in the table). Evaluation Criteria Evaluation 5: The rate of change in viscosity and the volume-based cumulative 50% particle size (D50) of the pigment are both less than 3%. Evaluation 4: The change rate of either viscosity or the volume-based cumulative 50% particle size (D50) of the pigment is between 3% and 5%. Evaluation 3: The change rate of either viscosity or the volume-based cumulative 50% particle size (D50) of the pigment is between 5% and 8%. Evaluation 2: The change rate of either viscosity or the volume-based cumulative 50% particle size (D50) of the pigment is between 8% and 10%. Evaluation 1: The change rate of either viscosity or the cumulative 50% particle size (D50) of the pigment by volume is 10% or more.

[0328] (Discharge stability) The ejection stability of the non-aqueous ink compositions in the examples, comparative examples, and reference examples was evaluated. Specifically, the non-aqueous ink compositions were filled into an inkjet printer (product name VersaArt RE-640, manufactured by Roland DG Corporation), and solid colors and fine lines were printed continuously on a recording medium (adhesive polyvinyl chloride film (IMAGin JT5829R: manufactured by MACtac)) in a bidirectional high-speed printing mode (360x720dpi) at a substrate surface temperature of 40°C. The presence or absence of dot defects, misaligned dots, and ink splatter was visually observed, and the number of occurrences was measured (indicated as "Ejection Stability" in the table). Evaluation Criteria Rating 5: Fine lines are reproduced correctly. Rating 4: Fine lines are generally reproduced correctly. Rating 3: There is a slight curvature in the thin lines. Rating 2: The point of impact was off, and a curve was visible. Rating 1: The point of impact is severely inaccurate, and it cannot reproduce thin lines.

[0329] (Cleaning recovery) For the non-aqueous ink compositions of the examples, comparative examples, and reference examples, we evaluated whether nozzle clogging in the print head could be resolved by the printer's cleaning operation. Specifically, using the above-mentioned inkjet printer equipped with a cleaning system (product name VersaArt RE-640, manufactured by Roland DG Corporation), the ink compositions of the examples and comparative examples were filled and printed in high-quality print mode (1440x720dpi) at 1.80m². 2After printing the solid color image, the printer was left at room temperature (25°C) for one week. Then, a nozzle check pattern was printed, and cleaning was performed until there were no more gaps (indicated as "Cleaning Recovery" in the table). Evaluation Criteria Rating 5: No omissions. Rating 4: Nozzle clogging is cleared in one cleaning cycle. Rating 3: Nozzle clogging can be cleared with 2-3 cleaning cycles. Rating 2: Nozzle clogging is cleared after 4-5 cleaning cycles. Rating 1: The nozzle clog was not cleared even after 6 cleaning cycles.

[0330] (Color stability (sedimentation)) The sedimentation properties of the non-aqueous ink compositions of the examples, comparative examples, and reference examples were evaluated. Specifically, 30 g of the non-aqueous ink composition was stored at room temperature for one month, and 1 g of the supernatant of the ink was taken before and after the test. This supernatant was then applied to a recording medium (adhesive polyvinyl chloride film (IMAGin JT5829R: MACtac)) using a bar coater #8 and dried in a 40°C oven. The value of the hue change ΔE before and after the test was evaluated. The hue was evaluated under the following conditions: Using an X-Rite eXact (X-Rite Corporation), with a viewing angle of 2°, a measurement range of 4 mmφ, and a D65 light source, L * a * , b * The values ​​were measured (indicated as "Color Stability (Settling)" in the table). Hue change ΔE is L before the test. *1 a *1 , b *1 , after the exam L *2 a *2 , b *2 Using the value of , it can be calculated using the following formula. ΔE=((L *1 -L *2 ) 2 +(a *1 -a *2 ) 2 +(b *1 -b *2 ) 2 ) (1 / 2) Evaluation Criteria Rating 5: ΔE is less than 2.0. Evaluation 4: ΔE is less than 2.5 or greater than 2.0. Evaluation 3: ΔE is less than 3.0 and greater than or equal to 2.5. Evaluation 2: ΔE is less than 3.5 or greater than 3.0. Evaluation 1: ΔE is 3.5 or higher.

[0331] (Surface dryness) The surface drying properties of the non-aqueous ink compositions of the Examples, Comparative Examples, and Reference Examples were evaluated. Specifically, the non-aqueous ink compositions of the Examples and Comparative Examples were printed as solid images on a recording medium (adhesive-backed polyvinyl chloride film (IMAGin JT5829R: MACtac)) using an inkjet printer (product name VersaArt RE-640, manufactured by Roland DG Corporation) in high-quality print mode (1440x720dpi), and the time it took to dry at 40°C was measured (indicated as "Surface Drying Properties" in the table). Evaluation Criteria Rating 5: Dries in less than 2 minutes. Rating 4: Dries in between 2 and 4 minutes. Rating 3: Dries in 4 to 6 minutes. Rating 2: Dries in 6 to 8 minutes. Rating 1: Dries in over 8 minutes.

[0332] (Smudge-proof) The non-aqueous ink compositions of the examples, comparative examples, and reference examples were evaluated for their bleeding properties. Specifically, using the above-mentioned inkjet printer (product name VersaArt RE-640, manufactured by Roland DG Corporation), images with solid areas of each color containing 6pt characters of a different color were printed on a recording medium (adhesive polyvinyl chloride film (IMAGin JT5829R: manufactured by MACtac)) in high-quality printing mode (1440x720dpi) at a substrate surface temperature of 50°C. The resulting prints were dried in a 60°C oven for 5 minutes, and the bleeding of the prints was observed visually and with a magnifying glass (x10). Evaluation Criteria Rating 5: No ink bleeding was observed under magnification. Rating 4: No ink bleeding was observed to the naked eye, and the 6pt lettering is clear. Rating 3: Slight ink bleeding was observed visually, but the design was not compromised. Evaluation 2: Although some ink bleeding was observed visually, the 6pt characters were still legible. Evaluation 1: Significant ink bleeding was visible to the naked eye, making the 6pt text illegible.

[0333] (weather resistance) The weather resistance of printed materials prepared using the non-aqueous ink compositions of the Examples, Comparative Examples, and Reference Examples was evaluated. The non-aqueous ink compositions of the Examples and Comparative Examples were used to print solid images on a recording medium (adhesive polyvinyl chloride film (IMAGin JT5829R: MACtac)) using an inkjet method with an inkjet printer (product name VersaArt RE-640, manufactured by Roland DG Corporation) in high-quality print mode (1440x720dpi), and dried at 40°C for 1 hour. The obtained data was placed inside a xenon weather meter (ATLAS Ci4000: manufactured by Toyo Seiki) and a cycle test was performed. The test conditions were based on JIS K-5600-7-7, with a black panel temperature of 63°C and a xenon lamp irradiance of 60 W / m². 2 The test chamber temperature was maintained at 38°C, and in segment 1, the humidity was maintained at 50% for 102 minutes, while in segment 2, water irradiation was performed for 18 minutes. This constituted one cycle. 50 cycles made up one set, and this cycle test was performed continuously for 10 sets. The hue change ΔE values ​​before and after the test were evaluated. Hue was evaluated under the following conditions: Using an X-Rite eXact (manufactured by X-Rite Corporation), the L*, a*, and b* values ​​were measured under the conditions of a viewing angle of 2°, a measurement range of 4 mmφ, and a D65 light source. Hue change ΔE is L before the test. *1 a *1 , b *1 , after the exam L *2 a *2 , b *2 Using the value of , it can be calculated using the following formula. ΔE=((L *1 -L *2) 2 +(a *1 -a *2 ) 2 +(b *1 -b *2 ) 2 ) (1 / 2) Evaluation Criteria Rating 5: ΔE is less than 5.0. Evaluation 4: ΔE is less than 10.0 and greater than or equal to 5.0. Evaluation 3: ΔE is less than 15.0 and greater than or equal to 10.0. Evaluation 2: ΔE is less than 20.0 and greater than or equal to 15.0. Evaluation 1: ΔE is 20.0 or higher.

[0334] [Table 22]

[0335] [Table 23]

[0336] [Table 24]

[0337] [Table 25]

[0338] [Table 26]

[0339] [Table 27]

[0340] [Table 28]

[0341] [Table 29]

[0342] In the table, "CI Pigment Green 7" is chlorinated copper phthalocyanine, and is a halogenated phthalocyanine pigment (density: 2.0 g / cm³). 3 This corresponds to ).

[0343] In the table, "CI Pigment Green 36" is brominated chlorinated copper phthalocyanine, a halogenated phthalocyanine pigment (density: 2.7 g / cm³). 3 This corresponds to ).

[0344] In the table, "CI Pigment Green 58" is zinc halide phthalocyanine and is classified as a halide phthalocyanine pigment.

[0345] In the table, "CI Pigment Blue 15:4" (Density: 1.6 g / cm³) 3 ) "CI Pigment Yellow 155" (Density: 1.45 g / cm³) 3 ) falls under the category of pigments that are not halogenated phthalocyanine pigments.

[0346] As can be seen from Tables 21-29, if the non-aqueous ink composition of the example contains halogenated phthalocyanine pigment A3 and the organic solvent is organic solvent B (at least one selected from the group consisting of alkylamide solvents (b1), cyclic amide solvents (b2), and lactone solvents (b3)), then even if it contains halogenated phthalocyanine pigment, it can be seen that it has high storage stability, color stability, and cleaning recovery properties.

[0347] In particular, among the non-aqueous ink compositions of Examples 3-8 to 3-14, in which the content of organic solvent B (alkylamide solvent) was changed, the non-aqueous ink compositions of Examples 3-9 to 3-14, in which the content of organic solvent B (alkylamide solvent) was 5% by mass or more, showed better color stability compared to Example 3-8.

[0348] Furthermore, in the non-aqueous ink compositions of Examples 3-15 to 3-24, 3-67, and 3-68, in which the type of organic solvent B was changed to an alkylamide solvent (b1), a cyclic amide solvent (b2), and a lactone solvent (b3), respectively, good storage stability and color stability were observed.

[0349] Furthermore, the non-aqueous ink compositions of Examples 3-25 to 3-27, in which the type of halogenated phthalocyanine pigment A3 was changed, exhibited good storage stability and color stability, similar to the non-aqueous ink composition of Example 3-1.

[0350] Furthermore, in the non-aqueous ink compositions of Examples 3-28 to 3-33, in which the volume-based cumulative 50% particle size (D50) and volume-based cumulative 90% particle size (D90) of the halogenated phthalocyanine pigment A3 were changed, Examples 3-28 to 3-31, in which D50 was 150 nm or less and D90 was 300 nm or less, showed better storage stability and color stability compared to the non-aqueous ink composition of Example 3-33.

[0351] Furthermore, in the non-aqueous ink compositions of Examples 3-34 to 3-37, in which the content of halogenated phthalocyanine pigment A3 was changed, the non-aqueous ink compositions of Examples 3-36 to 3-36, in which the content of pigment A3 was 0.1% by mass or more and 8.0% by mass or less, showed better storage stability and color stability compared to the non-aqueous ink composition of Example 3-37.

[0352] Furthermore, in the non-aqueous ink compositions of Examples 3-39 to 3-54, in which the content of resin with an intrinsic viscosity of 90 mL / g or more at 25°C was changed, the non-aqueous ink compositions of the examples in which the resin with an intrinsic viscosity of 90 mL / g or more at 25°C was in the range of 5% by mass or less of the total resin amount showed improved solid filling and discharge stability compared to the non-aqueous ink compositions of the examples in which it was in the range of more than 5% by mass.

[0353] Furthermore, in Examples 3-55 to 3-60 and 3-66, in which the type of pigment dispersant was changed, the non-aqueous ink compositions of Examples 3-56 to 3-60 and 3-66, which used a pigment dispersant having a basic group, showed improved storage stability and discharge stability compared to the non-aqueous ink composition of Example 3-55. Among these, the non-aqueous ink compositions of Examples 3-57 to 3-60 and 3-66, which had an amine value in the range of 20 mg KOH / g to 100 mg KOH / g, showed particularly improved storage stability and discharge stability.

[0354] Furthermore, in Examples 3-61 to 3-64, in which the pigment dispersant content was changed, the ink compositions of Examples 3-61 to 3-63, in which the pigment dispersant content was in the range of 5 parts by mass to 150 parts by mass per 100 parts by mass of pigment in the non-aqueous ink composition, showed improved surface drying properties compared to the ink composition of Example 3-64.

[0355] Furthermore, the ink compositions of Examples 3-68, which did not contain surfactants having a siloxane skeleton, showed a relatively slight decrease in bleeding properties.

[0356] On the other hand, the non-aqueous ink compositions of Comparative Examples 3-1 to 3-3, which do not contain organic solvent B (at least one selected from the group consisting of alkylamide solvents (b1), cyclic amide solvents (b2), and lactone solvents (b3)), do not exhibit the effects of the present invention.

[0357] Furthermore, the non-aqueous ink composition of Reference Example 3-1, which does not contain halogenated phthalocyanine pigment A3, exhibited good storage stability and color stability even without containing organic solvent B.

[0358] 4. Rating 2 The non-aqueous ink composition of Example 3-1, prepared as described above, was used for evaluation based on differences in water content. Specifically, the amount of water (exchanged ion water) shown in the table below (parts by mass per 100 parts by mass of the non-aqueous ink composition) was added to the non-aqueous ink composition of Example 3-1, prepared as described above, and the non-aqueous ink composition after water addition was evaluated in the same manner as described above. Note that the "water content" in the table is the value obtained using a Karl Fischer moisture meter 901 (manufactured by Metrohm Japan).

[0359] [Table 30]

[0360] As can be seen from Table 30, the lower the moisture content, the more effectively storage stability and dispensing stability can be improved.

Claims

1. A non-aqueous ink composition ejected by an inkjet method, containing a pigment, a pigment dispersant, and an organic solvent, The aforementioned pigment contains halogenated phthalocyanine pigment A3, The aforementioned organic solvent contains the following organic solvent B: The organic solvent B is at least one selected from the group consisting of alkylamide solvents (b1), cyclic amide solvents (b2), and lactone solvents (b3). When organic solvent B contains an alkylamide solvent (b1), the volume-based cumulative 50% particle size (D50) of the halogenated phthalocyanine pigment A3 is 30 nm or more and 207 nm or less. If organic solvent B does not contain alkylamide solvent (b1), the volume-based cumulative 50% particle size (D50) of the halogenated phthalocyanine pigment A3 is 30 nm or more and 150 nm or less. Non-aqueous ink composition.

2. The volume-based cumulative 90% particle size (D90) of the pigment A3 is between 50 nm and 300 nm. The non-aqueous ink composition according to claim 1.

3. The content of pigment A3 is 0.1% by mass or more and 8.0% by mass or less of the total amount of the non-aqueous ink composition. The non-aqueous ink composition according to claim 1 or 2.

4. The pigment A3 is at least one selected from the group consisting of chlorinated phthalocyanine pigment, brominated phthalocyanine pigment, and chlor-brominated phthalocyanine pigment. A non-aqueous ink composition according to any one of claims 1 to 3.

5. The pigment A3 is at least one selected from the group consisting of copper halide phthalocyanine pigment and zinc halide phthalocyanine pigment. A non-aqueous ink composition according to any one of claims 1 to 4.

6. The aforementioned organic solvent contains a glycol ether-based solvent. A non-aqueous ink composition according to any one of claims 1 to 5.

7. The water content is within the range of 1.0% by mass or less of the total amount of the non-aqueous ink composition. A non-aqueous ink composition according to any one of claims 1 to 6.

8. The aforementioned organic solvent contains a lactone-based solvent (b3). A non-aqueous ink composition according to any one of claims 1 to 7.

9. The pigment dispersant has a basic group. A non-aqueous ink composition according to any one of claims 1 to 8.

10. The amine value of the pigment dispersant is in the range of 20 mg KOH / g or more and 100 mg KOH / g or less. A non-aqueous ink composition according to any one of claims 1 to 9.

11. The content of the pigment dispersant is in the range of 5 parts by mass or more and 150 parts by mass or less per 100 parts by mass of pigment in the non-aqueous ink composition. A non-aqueous ink composition according to any one of claims 1 to 10.

12. Furthermore, it contains resin, The resin in question has an intrinsic viscosity of 90 mL / g or more at 25°C, and the amount of resin with an intrinsic viscosity of 90 mL / g or more is within 5% by mass of the total resin amount. A non-aqueous ink composition according to any one of claims 1 to 11.

13. The resin contains at least one selected from the group consisting of acrylic resins, vinyl chloride resins, cellulose resins, polyester resins, and polyurethane resins. The non-aqueous ink composition according to claim 12.

14. Dispense the non-aqueous ink composition according to any one of claims 1 to 13 onto the surface of a substrate using an inkjet method. Recording method.

15. Dispense the non-aqueous ink composition according to any one of claims 1 to 14 onto the surface of a substrate using an inkjet method. Method for manufacturing records.

16. An ink set comprising at least one non-aqueous ink composition according to any one of claims 1 to 14.

17. A printed layer of the non-aqueous ink composition according to any one of claims 1 to 14 is formed on the surface of a substrate. Records.

18. An inkjet recording apparatus that ejects a non-aqueous ink composition according to any one of claims 1 to 14 by an inkjet method, A storage mechanism for storing the non-aqueous ink composition, Inkjet ejection port, A tube through which the non-aqueous ink composition flows, Equipped with, The tube is connected to the storage mechanism and the inkjet ejection port and includes a valve mechanism for adjusting the flow path of the non-aqueous ink composition. Inkjet recording device.

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