Non-water-based ink compositions, ink groups, recording objects, recording methods, and methods for manufacturing recording objects.

Abstract

This invention provides a non-aqueous ink composition that, even when containing white or glossy pigments, possesses both high cleanability and surface drying properties on the substrate. The non-aqueous ink composition of this invention is an inkjet-printed composition containing a colorant and an organic solvent. The colorant contains a white or glossy pigment, and the organic solvent contains organic solvent A, which is selected from at least one of the group consisting of alkyl amide solvents (a1) and cyclic amide solvents (a2).

Description

Technical Field

[0001] This invention relates to a non-aqueous ink composition, an ink group, a recording object, a recording method, and a method for manufacturing the recording object. Prior Technology

[0002] As an ink composition, a non-aqueous ink composition is widely used, which is formed by dissolving or dispersing various colorants in a mixture with an organic solvent. This ink composition is coated or adhered to a substrate such as paper by means of inkjet printing or other methods, and the non-aqueous ink composition is dried, thereby obtaining text or images.

[0003] In some cases, for example, a non-aqueous ink composition containing white pigment is sprayed onto a transparent substrate using inkjet printing, followed by the spraying of colored ink. For this type of non-aqueous ink composition containing white pigment, in addition to spraying stability, concealment is also required.

[0004] For example, Patent Document 1 describes a non-aqueous ink composition containing a white pigment with a specific particle size and a glycol ether solvent. According to Patent Document 1, this non-aqueous ink composition exhibits excellent ejection stability and can produce records with excellent concealment.

[0005] Furthermore, there exist ink compositions (sometimes called metallic inks) capable of displaying images with metallic hues on printed materials such as substrates (recording media) or parts or the entire surface of such substrates covered with a coloring layer. For example, Patent Document 2 describes an ink composition containing a glossy pigment and a specific alkoxymethylamine solvent. According to Patent Document 2, this ink composition can produce recorded materials with excellent abrasion resistance and metallic gloss images. [Previous Technical Documents] [Patent Literature]

[0006] [Patent Document 1] Japanese Patent No. 6617410 [Patent Document 2] Japanese Patent Application Publication No. 2012-207119 Summary of the Invention

[0007] [The problem the invention aims to solve]

[0008] However, white pigments may contain metallic compounds such as titanium oxide. These metallic compounds have a higher density than other common pigments in ink compositions. As a result, the solid components, such as pigments, in non-water-based ink compositions can sometimes cause clogging in the inkjet nozzles.

[0009] Inkjet recording devices that eject non-aqueous ink compositions possess a cleaning and restoring function to clear nozzle clogging in such printheads. However, non-aqueous ink compositions containing white pigments are prone to clogging inside the printhead nozzles, which sometimes reduces the cleaning and restoring capability to clear such nozzle clogging. Furthermore, in this specification, the act of clearing nozzle clogging by means of the cleaning and restoring function of the inkjet recording device is sometimes abbreviated as cleaning and restoring capability.

[0010] In particular, non-aqueous ink compositions containing white pigments require concealment as described above. Therefore, for example, if the amount of non-aqueous ink composition ejected is increased in order to form a record with excellent concealment, the amount of non-aqueous ink composition on the substrate will also increase, thus requiring more time to dry.

[0011] Generally, non-aqueous ink compositions contain highly volatile solvents to improve surface drying properties on substrates. However, highly volatile solvents also tend to dry inside the inkjet head, leading to clogging of the nozzles and exacerbating the problem of reduced cleanability and reversibility.

[0012] Furthermore, glossy pigments contain, for example, metal powders or metal compounds. Therefore, glossy pigments have a higher density than other colorants in the ink composition. As a result, the solid components such as pigments in non-water-based ink compositions can sometimes cause clogging in the inkjet nozzles.

[0013] Inkjet recording devices that eject non-aqueous ink compositions have a cleaning and restoring function to clear nozzle clogging in such inkjet heads. However, non-aqueous ink compositions containing glossy pigments are prone to causing clogging in the nozzles of inkjet heads, which sometimes reduces the cleaning and restoring ability to clear such nozzle clogging.

[0014] In particular, if a non-aqueous ink composition containing glossy pigments is used, and the amount of non-aqueous ink composition ejected is increased in order to impart excellent gloss to the recording material, the amount of non-aqueous ink composition on the substrate will also increase, so drying time is required.

[0015] Generally, non-aqueous ink compositions contain highly volatile solvents to improve surface drying properties on substrates. However, highly volatile solvents also tend to dry inside the inkjet head, making the nozzles prone to clogging and exacerbating the problem of reduced cleanability and reversibility.

[0016] The purpose of this invention is to provide a non-aqueous ink composition that, even when containing white pigment, can combine high cleanability and surface drying properties on a substrate.

[0017] Furthermore, the present invention aims to provide a non-aqueous ink composition that, even when containing glossy pigments, can combine high cleanability and surface drying properties on a substrate. [Technical means to solve the problem]

[0018] In order to solve the above-mentioned problems, the inventors and others have made continuous research efforts and discovered that by using a specific organic solvent, the above-mentioned problems can be solved, thereby completing the present invention. Specifically, the following are provided.

[0019] (1) A non-aqueous ink composition comprising a colorant and an organic solvent, which is ejected by an inkjet method, wherein the colorant comprises a white pigment and the organic solvent comprises organic solvent A. Organic solvent A: selected from at least one of the group consisting of alkyl amide solvents (a1) and cyclic amide solvents (a2).

[0020] (2) The non-aqueous ink composition as described in (1), wherein the white pigment contains an inorganic oxide.

[0021] (3) The non-aqueous ink composition as described in (2), wherein the white pigment contains titanium oxide.

[0022] (4) The non-aqueous ink composition described in any one of (1) to (3), wherein the content of the white pigment is more than 8% by mass and less than 20% by mass of the total amount of the non-aqueous ink composition.

[0023] (5) The non-aqueous ink composition described in any one of (1) to (4) further contains a surfactant, wherein the surfactant contains a surfactant having a silicate skeleton, and the content of the surfactant having a silicate skeleton is more than 0.01% by mass and less than 1.0% by mass.

[0024] (6) The non-aqueous ink composition described in any one of (1) to (5) is used to form a bottom or top layer selected from the group consisting of black ink compositions, colored ink compositions, glossy ink compositions and transparent ink compositions.

[0025] (7) A non-aqueous ink composition comprising a glossy pigment and an organic solvent, which is ejected by inkjet printing, wherein the organic solvent comprises organic solvent A, which is selected from at least one of the group consisting of alkyl amide solvents (a1) and cyclic amide solvents (a2).

[0026] (8) The non-aqueous ink composition as described in (7), wherein the above-mentioned glossy pigment contains a metal-containing glossy pigment.

[0027] (9) The non-aqueous ink composition as described in (8), wherein the metal-containing glossy pigment comprises at least one selected from the group consisting of aluminum, aluminum alloys, indium, indium alloys, nickel, and nickel alloys.

[0028] (10) The non-aqueous ink composition as described in (9), wherein the metal-containing glossy pigment contains at least aluminum or an aluminum alloy.

[0029] (11) The non-aqueous ink composition described in any one of (8) to (10) wherein the volume-based cumulative 50% particle size (D50) of the metal-containing glossy pigment is 0.01 μm or more and 5.0 μm or less, and the volume-based cumulative 90% particle size (D90) of the metal-containing glossy pigment is 10.0 μm or less.

[0030] (12) The non-aqueous ink composition described in any of (8) to (11), wherein the metal-containing glossy pigment is a particle with a flat surface.

[0031] (13) The non-aqueous ink composition as described in (12), wherein the metal-containing glossy pigment comprises a plate-shaped or flake-shaped metal-containing glossy pigment.

[0032] (14) The non-aqueous ink composition as described in (13) wherein the thickness of the above-mentioned metal-containing glossy pigment in the form of a flat or flake is in the range of 5 nm to 5.0 μm.

[0033] (15) The non-aqueous ink composition described in any of (7) to (14), wherein the organic solvent further comprises an acetate-based solvent represented by the following formulas (2-3), [Chemistry 1] (In formula (2-3), X1 is an alkyl group, X2 is hydrogen or an alkyl group; n represents an integer from 1 to 4).

[0034] (16) The non-aqueous ink composition described in any one of (7) to (15) is used to form a base layer or surface layer selected from the group consisting of black ink compositions, colored ink compositions, glossy ink compositions and transparent ink compositions.

[0035] (17) The non-aqueous ink composition described in any one of (1) to (16), wherein the content of the organic solvent A is more than 1.0% by mass and less than 90.0% by mass of the total amount of the non-aqueous ink composition.

[0036] (18) The non-aqueous ink composition described in any one of (1) to (17), wherein the organic solvent A contains the alkyl amide solvent (a1).

[0037] (19) The non-aqueous ink composition as described in (18), wherein the alkylamide solvent is represented by the following general formula (1): [Chemistry 2] (In formula (1), R1 is a hydrogen or an alkyl group having 1 to 4 carbon atoms, and R2 and R3 each independently represent a hydrogen or an alkyl group having 1 to 4 carbon atoms).

[0038] (20) The non-aqueous ink composition as described in (19), wherein the alkyl acetamide solvent contains at least one selected from the group consisting of N,N-diethylmethylamine, N,N-diethylpropylamine and N,N-diethylacetamide.

[0039] (21) The non-aqueous ink composition described in any one of (1) to (17), wherein the organic solvent A contains the cyclic amide solvent (a2).

[0040] (22) The non-aqueous ink composition as described in (21), wherein the cyclic amide solvent is represented by the following general formula (2): [Chemistry 3] (In formula (2), R4 is an alkyl group with 3 to 5 carbon atoms, and R5 represents hydrogen or an alkyl or unsaturated hydrocarbon group with 1 to 4 carbon atoms).

[0041] (23) The non-aqueous ink composition as described in (22), wherein the cyclic acetylamine solvent contains at least one selected from the group consisting of ε-caprolactam, N-methyl-ε-caprolactam and N-vinylcaprolactam.

[0042] (24) The non-aqueous ink composition described in any one of (1) to (23), wherein the organic solvent further comprises at least one selected from the group consisting of glycol ether solvents, acetate solvents, cyclic esters, carbonates, diesters, lactates, amides and alcohols.

[0043] (25) The non-aqueous ink composition described in any one of (1) to (24), wherein the organic solvent contains a glycol ether solvent.

[0044] (26) The non-aqueous ink composition as described in (25), wherein the above-mentioned glycol ether solvent contains a glycol dialkyl ether.

[0045] (27) The non-aqueous ink composition as described in (25) or (26), wherein the above-mentioned glycol ether solvent contains a glycol monoalkyl ether.

[0046] (28) The non-aqueous ink composition described in any of (25) to (27), wherein the glycol ether solvent contains at least two solvents with different flash points.

[0047] (29) The non-aqueous ink composition described in any of (1) to (28) further contains a resin.

[0048] (30) The non-aqueous ink composition as described in (29), wherein the content of the above-mentioned resin is in the range of 0.1% by mass to 10.0% by mass of the total amount of the non-aqueous ink composition.

[0049] (31) The non-aqueous ink composition as described in (29) or (30), wherein the resin contains at least one of the group consisting of acrylic resins, vinyl chloride resins, polyurethane resins, polyester resins and cellulose resins.

[0050] (32) The non-aqueous ink composition described in any one of (29) to (31), wherein the non-aqueous ink composition is a white ink composition containing white pigment, and the content ratio of the resin to the white pigment is 0.20 to 1.00.

[0051] (33) An ink group comprising a non-aqueous ink composition as described in any one of (1) to (32).

[0052] (34) An ink group comprising a non-aqueous ink composition as described in any one of (1) to (32), wherein the non-aqueous ink composition is a white ink composition containing a white pigment, wherein the non-aqueous ink composition and at least one of the group consisting of a black ink composition, a colored ink composition, a glossy ink composition and a transparent ink composition are simultaneously sprayed onto the surface of a substrate by inkjet.

[0053] (35) An ink group comprising a non-aqueous ink composition as described in any one of (1) to (32), wherein the non-aqueous ink composition is a glossy ink composition containing a glossy pigment, wherein the non-aqueous ink composition and at least one of the group consisting of a black ink composition, a colored ink composition, a white ink composition and a transparent ink composition are simultaneously sprayed onto the surface of a substrate by inkjet.

[0054] (36) A recording material formed on the surface of a substrate by forming a recording layer of a non-aqueous ink composition as described in any one of (1) to (32).

[0055] (37) A recording method comprising spraying a non-aqueous ink composition as described in any one of (1) to (32) onto the surface of a substrate by inkjet printing.

[0056] (38) A method for manufacturing a record, wherein a non-aqueous ink composition as described in any one of (1) to (32) is sprayed onto the surface of a substrate by inkjet spraying. [Effects of the Invention]

[0057] Even when the non-aqueous ink composition of the present invention contains white pigment, it can still achieve both high cleanability and surface drying properties on the substrate.

[0058] Even when the non-aqueous ink composition of the present invention contains glossy pigments, it can still achieve both high cleanability and surface drying properties on the substrate. Implementation

[0059] The following describes specific embodiments of the present invention in detail. However, the present invention is not limited to any of the following embodiments and can be implemented by appropriate modifications within the scope of the purpose of the present invention. Furthermore, in this specification, the notation "~" means "above" or "below".

[0060] ≪1.Outline≫ One embodiment of the present invention is a non-aqueous ink composition containing pigments, pigment dispersants, and organic solvents, which is produced by inkjet printing. Here, in this specification, the term "non-aqueous ink composition" means an ink composition containing organic solvents that is not intentionally made to contain water, unlike aqueous ink compositions which are mainly composed of water.

[0061] Furthermore, the ink composition of this embodiment (including the non-aqueous ink compositions of the first and second embodiments described below) is preferably an ink composition in which a recording is obtained by drying (evaporating) an organic solvent. Specifically, this ink composition forms a recording by drying (evaporating) volatile components such as organic solvents contained in the ink composition, thereby causing their residues to accumulate on the surface of the substrate. This ink composition differs from active energy line curing ink compositions that polymerize and harden on a substrate by irradiation with active energy lines such as ultraviolet light. Active energy line curing ink compositions contain polymerizable compounds as essential components, but ink compositions in which a recording is obtained by drying (evaporating) an organic solvent contain organic solvents but do not necessarily contain polymerizable compounds as essential components; they may or may not contain polymerizable compounds.

[0062] Furthermore, the organic solvent is characterized by containing the following organic solvent A.

[0063] Organic solvent A: selected from at least one of the group consisting of alkyl amide solvents (a1) and cyclic amide solvents (a2).

[0064] The specific embodiments of the present invention will be described in detail below.

[0065] ≪1-1. Non-aqueous ink composition of the first embodiment≫ The non-aqueous ink composition of the first embodiment of this invention is ejected by inkjet printing and contains a colorant including white pigment and an organic solvent.

[0066] Furthermore, the organic solvent is characterized by containing the following organic solvent A.

[0067] Organic solvent A: selected from at least one of the group consisting of alkyl amide solvents (a1) and cyclic amide solvents (a2).

[0068] By using an organic solvent A (selected from at least one of the group consisting of alkyl amide solvents (a1) and cyclic amide solvents (a2)), even non-aqueous ink compositions containing white pigments can effectively remove clogging in the nozzles of the inkjet head, thereby improving the cleanability and reversibility of the non-aqueous ink composition.

[0069] Furthermore, according to the inventors' understanding, although organic solvent A exhibits high drying properties on the substrate surface, it has low volatility within the plastic supply (e.g., a supply tube). Therefore, non-aqueous ink compositions containing organic solvent A not only maintain clean-recovery properties but also yield recordings with excellent surface drying properties. The reason for the higher drying properties of organic solvent A on the substrate surface and the lower volatility within the plastic supply is that organic solvent A has low permeability to plastic, and the boiling point of the organic solvent itself is not necessarily related to its volatility within the plastic supply.

[0070] Furthermore, the water content in the non-aqueous ink composition of this embodiment is preferably 5.0% by mass or less, more preferably 1.0% by mass or less, and even more preferably 0.5% by mass or less. If moisture originating from raw materials or from atmospheric moisture during the manufacturing process is introduced, the storage stability or ejection stability of the non-aqueous ink composition may deteriorate, or solids may form due to the components contained in the non-aqueous ink composition. By reducing the water content in the non-aqueous ink composition to be as moisture-free as possible (without intentionally introducing moisture), storage stability and cleanability can be improved more effectively.

[0071] The components contained in the non-aqueous ink composition of this embodiment will be described below.

[0072] [Organic solvents] Organic solvents can disperse or dissolve the components contained in the non-aqueous ink composition of this embodiment. The organic solvent contains organic solvent A (selected from at least one of the group consisting of alkyl amide solvents (a1) and cyclic amide solvents (a2)).

[0073] (1) Alkylamine solvents Alkylamide solvents are compounds having an alkyl (CnH2n+1-) and a -C(=O)-N- group (amide bond), including solvents containing hydrogen or alkyl and -C(=O)-N- groups. Alkylamide solvents, for example, are preferably those having the following structure.

[0074] [Chemistry 4] (In formula (1), R1 is a hydrogen or an alkyl group having 1 to 4 carbon atoms, and R2 and R3 each independently represent a hydrogen or an alkyl group having 1 to 4 carbon atoms).

[0075] Furthermore, R2 and R3 in formula (1) are preferably alkyl groups having 1 to 4 carbon atoms, and more preferably alkyl groups having 2 to 4 carbon atoms.

[0076] Examples of alkylamide solvents include N,N-diethylmethylamine, N,N-diethylacetamide, N,N-dipropylmethylamine, N,N-dibutylmethylamine, N,N-diethylpropane, N,N-dipropylpropane, N-ethylmethylamine, and N-ethylacetamide. From the viewpoint of particularly maximizing the effects of the present invention, it is preferable to contain at least one solvent selected from the group consisting of N,N-diethylmethylamine, N,N-diethylpropane, and N,N-diethylacetamide.

[0077] There is no particular limitation on the content of alkyl amide solvent (a1), but the lower limit of the content of alkyl amide solvent (a1) is preferably more than 1% by mass of the total amount of the non-aqueous ink composition, more preferably more than 5% by mass, and even more preferably more than 8% by mass.

[0078] The upper limit of the content of alkyl amide solvent (a1) is preferably less than 90% by mass of the total amount of the non-aqueous ink composition, more preferably less than 80% by mass, and even more preferably less than 75% by mass.

[0079] (2) Cyclic amide solvents The term "cyclic amide solvent" (a2) refers to a solvent having a cyclic structure with -C(=O)-N- groups on that cyclic structure. Cyclic amide solvents, for example, preferably have the following structure.

[0080] [Chemistry 5] (In formula (2), R4 is an alkyl group with 3 to 5 carbon atoms, and R5 represents hydrogen or an alkyl or unsaturated hydrocarbon group with 1 to 4 carbon atoms.)

[0081] The term "unsaturated hydrocarbon group" refers to hydrocarbon groups such as vinyl groups that contain at least one or more multiple bonds.

[0082] Furthermore, R5 is preferably hydrogen or an alkyl or unsaturated hydrocarbon group having 1 to 3 carbon atoms, and more preferably hydrogen or an alkyl or unsaturated hydrocarbon group having 1 to 2 carbon atoms.

[0083] As a cyclic acetylamine solvent (a2), examples include: N-methylcaprolactone, N-acetylopeptylcaprolactone, ε-caprolactone, N-vinylcaprolactone, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-ethyl-ε-caprolactone, N-propyl-ε-caprolactone, N-methyl-ε-caprolactone, etc. Preferably, it contains at least one selected from the group consisting of ε-caprolactone, N-methylcaprolactone, and N-vinylcaprolactone.

[0084] There is no particular limitation on the content of the cyclic amide solvent (a2), but the lower limit of the content of the cyclic amide solvent (b2) is preferably more than 1% by mass of the total amount of the non-aqueous ink composition, more preferably more than 5% by mass, and even more preferably more than 8% by mass.

[0085] The upper limit of the content of cyclic amide solvent (a2) is preferably less than 90% by mass of the total amount of non-aqueous ink composition, more preferably less than 80% by mass, and even more preferably less than 75% by mass.

[0086] Of the organic solvents A, it is preferable to use one that contains an alkyl amide solvent (a1). If it contains an alkyl amide solvent (a1), it combines cleaning and restoring properties with surface drying on the substrate, and has good component compatibility with inkjet recording devices.

[0087] The effects of this invention are fully realized by including at least one of alkylamide solvents (a1) and cyclic amide solvents (a2) in organic solvent A, but two or more solvents in organic solvent A can also be mixed. By mixing two or more solvents, the balance of storage stability, component suitability, surface drying properties, and cleaning and recovery properties can be adjusted arbitrarily. When two or more solvents in organic solvent A are mixed, the lower limit of the total content of organic solvent A is preferably 1.0% by mass or more of the total amount of the non-aqueous ink composition, more preferably 5.0% by mass or more, and even more preferably 10.0% by mass or more. The upper limit of the total content of organic solvent A is preferably 90.0% by mass or less of the total amount of the non-aqueous ink composition.

[0088] (4) Other organic solvents The non-aqueous ink composition of this embodiment may also contain organic solvents other than organic solvent A mentioned above. Specifically, examples include: dialkyl ethers of glycols with alkyl-substituted OH groups at both ends, monoalkyl ethers of glycols with alkyl-substituted OH groups at one end, carbonates, cyclic esters, etc.

[0089] Examples of glycol ether solvents include: glycol dialkyl ethers in which the OH groups at both ends of a glycol are alkylated, or glycol monoalkyl ethers in which the OH groups at one end of a glycol are alkylated. Examples of glycol ether solvents include those represented by the following formula (5) that contain at least one glycol monoalkyl ether and glycol dialkyl ether.

[0090] R 8-(-OR 9) nOR 10···(1-3) (In formulas (1-3), R8 and R10 are independently hydrogen or alkyl groups with 1 to 8 carbon atoms that may have branches, and R9 represents an alkyl group with 1 to 4 carbon atoms that may have branches. n represents an integer of 1 to 6.)

[0091] Examples of glycol ether solvents include: ethylene glycol mono-n-butyl ether, ethylene glycol mono-isobutyl ether, ethylene glycol mono-tert-butyl ether, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monoisopropyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol monoisobutyl ether, diethylene glycol mono-tert-butyl ether, diethylene glycol mono-2-ethylhexyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monoisopropyl ether, triethylene glycol mono-n-butyl ether, triethylene glycol monoisobutyl ether, and triethylene glycol mono-tert-butyl ether. Triethylene glycol mono-2-ethylhexyl ether, tetraethylene glycol monomethyl ether, propylene glycol mono-n-butyl ether, propylene glycol monoisobutyl ether, propylene glycol monotert-butyl ether, propylene glycol mono-2-ethylhexyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoisopropyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol monoisobutyl ether, dipropylene glycol monotert-butyl ether, dipropylene glycol mono-2-ethylhexyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monoisopropyl ether, tripropylene glycol mono-n-butyl ether, tripropylene glycol monoisobutyl ether, tripropylene glycol mono-2-ethylhexyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monoisopropyl ether, tripropylene glycol mono-n-butyl ether, tripropylene glycol monoisobutyl ether, tripropylene glycol mono-2-ethylhexyl ether Tertiary butyl ether, tetrapropylene glycol monomethyl ether, tetrapropylene glycol monoethyl ether, tetrapropylene glycol monopropyl ether, tetrapropylene glycol monoisopropyl ether, tetrapropylene glycol mono-n-butyl ether, tetrapropylene glycol monoisobutyl ether, tetrapropylene glycol monotertiary butyl ether, tetrapropylene glycol mono-2-ethylhexyl ether and other alkyl glycol monoalkyl ethers; 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 Dialkyl ethers of polyols, including triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol ethyl methyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol ethyl 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.

[0092] Examples of suitable alternatives include: 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.

[0093] Furthermore, it is preferable to combine two or more glycol ether solvents with different flash points. By containing a glycol ether solvent with a high flash point (e.g., above 70°C), a non-aqueous ink composition with high clean-recovery properties is obtained. By containing a glycol ether solvent with a low flash point (e.g., below 70°C), a non-aqueous ink composition with high surface drying properties on a substrate is obtained. By containing both glycol ether solvents with a flash point above 70°C and glycol ether solvents with a flash point below 70°C, a non-aqueous ink composition that effectively combines high clean-recovery properties with surface drying properties on a substrate is obtained, thus demonstrating the effects of the present invention particularly effectively.

[0094] Furthermore, it may also contain solvents other than glycol ether solvents. Specifically, examples include: cyclic esters such as γ-butyrolactone, δ-valerolactone, δ-caprolactone, ε-caprolactone, γ-valerolactone, γ-caprolactone, γ-heptanolactone, γ-octanolactone, γ-nonanolactone, γ-decanolactone, γ-undecanoic acid lactone, δ-heptanolactone, δ-octanolactone, δ-nonanolactone, δ-decanolactone, and δ-undecanoic acid lactone; carbonates such as propylene carbonate and ethylene carbonate; acezolidinone solvents such as 3-methyl-2-acezolidinone, 3-ethyl-2-acezolidinone, and N-vinylmethylacezolidinone; 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, and propylene glycol methyl ether acetate. Acetic acid ester solvents such as esters, dipropylene glycol methyl ether acetate, 1-methoxy-2-propane acetate, 2-methylbutyl acetate, 3-methoxybutyl ether acetate, and cyclohexyl acetate; acetamide solvents that differ from alkyl acetamide solvents (a1) or cyclic acetamide solvents (a2) such as 3-methoxypropionic acid, 3-butoxypropionic acid, N,N-dimethyl-3-methoxypropionic acid, N,N-dibutyl-3-methoxypropionic acid, N,N-dibutyl-3-butoxypropionic acid, and N,N-dimethyl-3-butoxypropionic acid; alkyl alcohols with 1 to 5 carbon atoms such as methanol, ethanol, n-propanol, isopropanol, n-butanol, dibutanol, tert-butanol, isobutanol, and n-pentanol; 3-methoxy... Monohydric alcohol solvents such as 3-methyl-1-butanol, 3-methoxy-1-propanol, 1-methoxy-2-propanol, and 3-methoxy-n-butanol; ketones or ketol alcohols such as acetone, diacetone alcohol, methyl ethyl ketone, methyl n-propyl ketone, methyl isopropyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, methyl hexyl ketone, methyl isopentyl ketone, diethyl ketone, ethyl n-propyl ketone, ethyl isopropyl ketone, ethyl n-butyl ketone, di-n-propyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl cyclohexanone, isophorone, and acetone; ethers such as tetrahydrofuran and dialkylene; copolymers of polyethylene glycol and polypropylene glycol; ethylene glycol, propylene glycol, and diethylene glycol. Diols such as alcohols, dipropylene glycol, 1,3-propanediol, isobutylene glycol, triethylene 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-butanediol, 3-methyl-1,5-pentanediol, and 2-methyl-2,4-pentanediol; triols such as glycerol, trimethylolethane, trimethylolpropane, and 1,2,6-hexanetriol; and tetraols such as meso-erythritol and pentaerythritol.Alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-ethylethanolamine, n-butylethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, and n-butyldiethanolamine; acetates such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, and octyl acetate; lactates such as methyl lactate, ethyl lactate, butyl lactate, propyl lactate, ethylhexyl lactate, pentyl lactate, and isoamyl lactate; and hexane, isohexane, n-nonane, isononane, dodecane, and isodecane. Saturated hydrocarbons such as diane; unsaturated hydrocarbons such as 1-hexene, 1-heptene, and 1-octene; cyclic unsaturated hydrocarbons such as cyclohexene, cycloheptene, cyclooctene, 1,1,3,5,7-cyclooctatetraene, and cyclododecene; aromatic hydrocarbons such as benzene, toluene, and xylene; morpholines such as N-methylmorpholine, N-ethylmorpholine, and N-methoxymorpholine; terpene solvents; and dicarboxylate esters such as dimethyl oxalate, diethyl oxalate, dimethyl malonate, diethyl malonate, dimethyl succinate, diethyl succinate, dimethyl glutarate, and diethyl glutarate. Preferably, it contains at least one solvent selected from the group consisting of glycol ether solvents, acetate solvents, cyclic esters, carbonates, dicarboxylate esters, lactates, amides, and alcohols. Preferably, a solvent with a suitable HLB (Hydrophile-Lipophile Balance) value is selected based on the resin or dispersant being combined.

[0095] There are no particular restrictions on the content of other organic solvents, but the lower limit of the content of other organic solvents is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more. The upper limit of the content of other organic solvents is preferably 85% by mass or less, more preferably 80% by mass or less, and even more preferably 75% by mass or less.

[0096] [color material] The non-aqueous ink composition of this embodiment contains a colorant. The colorant contains a white pigment. The white pigment will be described below.

[0097] (White pigment) As a white pigment, there are no particular limitations. Examples include: white inorganic pigments containing metal compounds such as CI pigments 6, 18, 21, titanium dioxide, zinc oxide, silicon dioxide, calcium carbonate, magnesium carbonate, zinc sulfide, precipitated barium sulfate, antimony oxide, and zirconium oxide, or clay and pearlescent pigments.

[0098] The white pigment is preferably an inorganic oxide, and more preferably a titanium oxide. A non-aqueous ink composition containing inorganic oxides (more preferably a titanium oxide) yields recordings with superior concealment. In particular, a higher content of white pigment results in even better concealment, but it also tends to cause clogging in the printhead nozzles, further reducing cleanability. However, by containing organic solvent A (selected from at least one of alkylamide solvents (a1) and cyclic amide solvents (a2)), even a non-aqueous ink composition containing titanium oxide can effectively remove clogging in the printhead nozzles and improve the cleanability of the non-aqueous ink composition.

[0099] Commercially available titanium oxides can also be used, such as: STR-100N (trade name, manufactured by Sakai Chemical Industry Co., Ltd., rutile type), TTO-51A, TTO-55A, TTO-55A, TTO-80A, MPT-140, MPT-141 (trade name, manufactured by Ishihara Sangyo Co., Ltd., rutile type), MKR-1 (trade name, manufactured by Sakai Chemical Industry Co., Ltd., rutile type), KA-10 (trade name, Titanium oxide). Kogyo Co., Ltd. manufactures (anatase type), RDI-S, RODI, RDO, RDE2, EDDI (trade name, manufactured by SACHTLEBEN, rutile type), JR-301, JR-403, JR-405, JR-600A, JR-605, JR-600E, JR-603, JR-805, JR-800, JR-806, JR-701, JRNC, JR (trade name, manufactured by Tayca Co., Ltd., rutile type), JA-1, JA-C, JA-3 (trade name, manufactured by Tayca Co., Ltd., anatase type), etc.

[0100] There is no particular limitation on the average particle size of the white pigment, but the upper limit of the volumetric cumulative 50% particle size (D50) is preferably 500 nm or less, more preferably 450 nm or less, and even more preferably 400 nm. This effectively suppresses the aggregation of white pigment in the non-aqueous ink composition, thereby improving cleanability and ejection stability. The lower limit of the volumetric cumulative 50% particle size (D50) is preferably 50 nm or more, and even more preferably 100 nm or more. By ensuring that the volumetric cumulative 50% particle size (D50) of the white pigment falls within this range, the preservation stability of the non-aqueous ink composition can be improved.

[0101] Furthermore, in this specification, the term "cumulative 50% volumetric particle size (D50)" refers to the particle size at which the cumulative volume, calculated from the smallest diameter side, reaches 50%. "Cumulative 50% volumetric particle size (D50)" is sometimes also referred to as "volume average particle size D50" or "median particle size." "Cumulative 50% volumetric particle size (D50)" can be measured using instruments such as the "FPIA-3000S" manufactured by Sysmex Corporation or the "SALD 7500nano" laser diffraction particle size analyzer manufactured by Shimadzu Corporation.

[0102] There is no particular limitation on the content of white pigment, but the lower limit of the white pigment content is preferably 8% by mass or more of the total amount of the non-water-based ink composition, more preferably 9% by mass or more, and even more preferably 10% by mass or more. By making the white pigment content 8% by mass or more, a non-water-based ink composition with superior concealment can be obtained.

[0103] Especially when the white pigment content is high, the recorded image exhibits superior concealment; however, this also tends to cause clogging in the inkjet head nozzles, further reducing cleanability and reproducibility. However, by using an organic solvent A (selected from at least one of the group consisting of alkyl amide solvents (a1) and cyclic amide solvents (a2)), even non-aqueous ink compositions containing a high amount of white pigment can effectively remove clogging from the inkjet head nozzles, improving the cleanability and reproducibility of the non-aqueous ink composition.

[0104] The upper limit of the white pigment content is preferably 20% by mass or less, more preferably 18% by mass or less, and even more preferably 16% by mass or less. This can more effectively improve the cleaning and restoring properties of non-water-based ink compositions.

[0105] Furthermore, the non-water-based ink composition of this embodiment may also contain colorants other than white pigments. Examples of colorants other than white pigments include metallic pigments containing elemental metals or alloys such as aluminum, silver, gold, nickel, chromium, tin, zinc, indium, titanium, and copper.

[0106] [Pigment Dispersant] In the non-aqueous ink composition of this embodiment, a pigment dispersant may also be used as needed. Any pigment dispersant used in the non-aqueous ink composition may be used as the dispersant. A polymeric dispersant is preferred. This type of dispersant has a main chain comprising polyester, polyacrylic acid, polyurethane, polyamine, polycaprolactone, etc., and has polar groups such as amine, carboxyl, ternary, and hydroxyl groups on its side chains. As a polyacrylic acid-based dispersant, for example, Disperbyk-2000, 2001, 2008, 2009, 2010, 2020, 2020N, ​​2022, 2025, 2050, 2070, 2095, 2150, 2151, 2155, 2163, 2164; BYKJET-9130, 9131, 9132, 9133, 9151 (manufactured by BYK-Chemie); Efka PX4310, PX4320, PX4330, PA4401, 4402, PA4403, 4570, 7411, 7477, PX4700, PX4701 (manufactured by BASF); TREPLUS D-1200, D-1410, D-1420, MD-1000 (manufactured by Otsuka Chemical Co., Ltd.); Flowlen DOPA-15BHFS, 17HF, 22, G-700, 900, NC-500, GW-1500 (manufactured by Kyoeisha Chemical Co., Ltd.), etc. As polycaprolactone-based dispersants, for example, Ajisper PB821, PB822, PB881 (manufactured by Ajinomoto Fine-Techno Co., Ltd.); Hinoact KF-1000, T-6000, T-7000, T-8000, T-8000E, T-9050 (manufactured by Sichuan 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 Co., Ltd.); TEGO Dispers 652, 655, 685, 688, 690 (manufactured by Evonik Japan), etc.Preferred dispersants include BYKJET-9130, 9131, 9132, 9133, 9151; Efka PX4310, PX4320, PX4330, PX4700, PX4701; Solsperse 20000, 24000, 32000, 33000, 33500, 34000, 35200, 39000, 71000, 76500, 86000, 88000, J180, J200; and TEGO Disperses 655, 685, 688, 690. A single dispersant or a mixture thereof may be used.

[0107] There is no particular limitation on the content of the pigment dispersant. However, relative to 100 parts by weight of pigment in the non-aqueous ink composition, the lower limit of the pigment dispersant content is preferably 5 parts by weight or more, more preferably 15 parts by weight or more, and even more preferably 20 parts by weight or more. Relative to 100 parts by weight of pigment in the non-aqueous ink composition, the upper limit of the pigment dispersant content is preferably 150 parts by weight or less, more preferably 125 parts by weight or less, and even more preferably 100 parts by weight or less.

[0108] [Resin] The non-aqueous ink composition of this embodiment may or may not contain resin. By containing resin, the fixation, water resistance, and elongation of the recording layer formed from the non-aqueous ink composition can be improved. Furthermore, the gloss of the obtained recorded material can be improved.

[0109] The resin is not particularly limited, and for example, 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 (silicone) resins, acrylamide resins, epoxy resins, or copolymers or mixtures thereof can be used. Preferably, the resin includes acrylic resins, vinyl chloride resins, cellulose resins, polyester resins, and polyurethane resins.

[0110] There are no particular limitations on acrylic resins as long as they contain (meth)acrylate monomers as the main component of the monomers. Acrylic resins can be homopolymers of a single free radical polymerizable monomer, or copolymers of any two or more free radical polymerizable monomers. The acrylic resin used in the non-aqueous ink composition of this embodiment is preferably a homopolymer of methyl methacrylate, 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)acrylate resins include, for example, Rohm & Haas's "Paraloid B99N," "Paraloid B60," "Paraloid B66," and "Paraloid B82."

[0111] Vinyl chloride-based resins can be homopolymers containing vinyl chloride monomers, or copolymers of any two or more polymerizable monomers. Examples of vinyl chloride-based copolymers include vinyl chloride-vinyl acetate copolymer resins. Vinyl chloride-vinyl acetate copolymer resins are polymers of vinyl chloride monomers and vinyl acetate monomers. Examples of vinyl chloride-vinyl acetate copolymer resins include vinyl chloride-vinyl acetate copolymers, vinyl chloride / vinyl acetate / maleic acid copolymers, vinyl chloride / vinyl acetate / vinyl alcohol copolymers, vinyl chloride / vinyl acetate / hydroxyalkyl acrylate copolymers, and mixtures thereof. As the aforementioned vinyl chloride-vinyl acetate copolymer resin, the following products purchased from Nissin Chemical Industry Co., Ltd. may be used: "SOLBIN C", "SOLBIN CL", "SOLBIN CNL", "SOLBIN CLL", "SOLBIN CLL2", "SOLBIN C5R", "SOLBIN TA2", "SOLBIN TA3", "SOLBIN A", "SOLBIN AL", "SOLBIN TA5R", "SOLBIN M5", etc.

[0112] Vinyl chloride-vinyl acetate copolymer resin can be obtained by polymerizing vinyl chloride monomer and vinyl acetate monomer. The polymerization method can be any previously known polymerization method. Emulsion polymerization or suspension polymerization is preferred, and suspension polymerization is even more preferred.

[0113] Cellulose-based resins refer to resins that have a cellulose backbone obtained by introducing functional groups from cellulose as a raw material through biological or chemical means. Examples of cellulose-based resins include cellulose acetate butyrate resin, cellulose acetate propionate resin, cellulose acetate propionate butyrate resin, cellulose acetate alkylate resin, cellulose acetate resin, nitrocellulose resin, and mixtures thereof. As the aforementioned cellulose resins, products purchased from EASTMAN Corporation under the trade names "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" can be used.

[0114] Polyester resins refer to those that contain at least structural units obtained by the condensation polymerization of alcohol and carboxylic acid components. Polyester resins may also include modified polyester resins. As polyester resins, those available from Toyobo under the trade names "VYLON226", "VYLON270", "VYLON560", "VYLON600", "VYLON630", "VYLON660", "VYLON885", "VYLONGK250", "VYLONGK810", "VYLONGK890", etc., or from Unitika under the trade names "elitleUE-3200", "elitleUE-3285", "elitleUE-3320", "elitleUE-9800", "elitleUE-9885", etc.

[0115] Polyurethane resins refer to resins that contain at least structural units obtained by copolymerizing an alcohol component with an isocyanate component. Polyurethane resins may also include polyurethane resins modified with polyester, polyether, or caprolactone. As the aforementioned polyurethane resin, one can use products such as "Ureano KL-424", "Ureano KL-564", "Ureano KL-593", "Ureano 3262" purchased from Arakawa Chemical Industry Co., Ltd., or products such as "PANDEX 372E", "PANDEX 390E", "PANDEX 394E", "PANDEX 304", "PANDEX 305E", "PANDEX P-870", "PANDEX P-910", "PANDEX P-895", "PANDEX 4030", "PANDEX 4110" purchased from DIC Corporation.

[0116] Furthermore, these acrylic resins, vinyl chloride resins, cellulose resins, polyester resins, and polyurethane resins can be used individually, but it is preferable to use two types in combination, and even more preferably, a resin obtained by mixing acrylic resins and vinyl chloride resins. By controlling the content ratio of acrylic resins to vinyl chloride resins, the non-aqueous ink composition can be made to meet the required requirements for color development, drying properties, coating properties, and printability. When mixing acrylic resins and vinyl chloride resins, there are no particular restrictions on the mixing ratio, which can be appropriately varied.

[0117] 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. This further improves the surface drying properties of the obtained record. 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. This more effectively removes clogging from the inkjet head nozzles, further improving cleanability and reversibility, and enhancing the storage stability of the non-aqueous ink composition.

[0118] Preferably, the ratio of resin content to white pigment content (resin content in the non-aqueous ink composition / white pigment content in the non-aqueous ink composition) is controlled. Specifically, the lower limit of the resin content to white pigment content ratio is preferably 0.20 or higher, more preferably 0.23 or higher, and even more preferably 0.25 or higher. This improves the concealment of the recorded material. Furthermore, the upper limit of the resin content to white pigment content ratio is preferably 1.00 or lower, more preferably 0.90 or lower, and even more preferably 0.80 or lower. This improves the ejection stability of the non-aqueous ink composition.

[0119] [Surfactants] In the non-aqueous ink composition of this embodiment, a surfactant may be added in order to suppress the volatilization of the non-aqueous ink composition inside the machine, such as in the nozzle or tube, to prevent curing, or to prevent redissolution during curing; to reduce surface tension and improve wettability with the recording medium (substrate); to suppress the ink composition from spreading on the substrate; to improve the abrasion resistance of the coating; and to enhance the gloss of the recorded material.

[0120] Regarding surfactants, examples include: nonionic polyoxyalkylene ethers such as 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 Oils & Fats Co., Ltd.), EMULGEN 106, 108, 707, 709, A-90, A-60 (manufactured by Kao Corporation), Flowlen G-70, D-90, TG-740W (manufactured by Kyoei Chemical Co., Ltd.), and POEM J-0081HV (manufactured by Richen Vitamin Co., Ltd.); and aliphatic phosphate esters such as ADEKA TOL. NP-620, NP-650, NP-660, NP-675, NP-683, NP-686, ADEKA COL CS-141E, TS-230E (manufactured by ADEKA Corporation), SORGEN 30V, 40, TW-20, TW-80, NOIGEN CX-100 (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.), etc.; as fluorinated surfactants, fluorinated modified polymers are preferred. Specific examples include: BYK-340 (BYK-Chemie... As silicone surfactants with a siloxane backbone, polyester-modified silicone or polyether-modified silicone are preferred. Specific examples include: BYK-313, 315N, 322, 326, 331, 347, 348, BYK-UV3500, 3510, 3530, 3570 (all manufactured by BYK-Chemie Japan). As acetylene glycol surfactants, specific examples include: Surfynol (registered trademark) 82, 104, 465, 485, TG (all manufactured by AIR PRODUCTS JAPAN), Olfine (registered trademark) STG, E1010 (all manufactured by Nissin Chemical Co., Ltd.). The surfactants are not limited to the above; any anionic, cationic, amphoteric, or nonionic surfactant can be used.

[0121] Among them, the surfactant is preferably a surfactant containing a silicate skeleton. If the non-aqueous ink contains a surfactant with a silicate skeleton, the printed text will have less bleed and improved abrasion resistance.

[0122] As surfactants with a siloxane backbone, polyester-modified silicone or polyether-modified silicone are preferred. Specific examples include BYK-313, 315N, 322, 326, 331, 347, 348, BYK-UV3500, 3510, 3530, and 3570 (all manufactured by BYK-Chemie Japan).

[0123] The non-aqueous ink composition of this embodiment may also contain a surfactant with a siloxane backbone and a surfactant different from the surfactant with a siloxane backbone.

[0124] In the non-aqueous ink composition of this embodiment, the content of surfactant is not particularly limited. Preferably, the lower limit of the surfactant content is 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more. Preferably, the lower limit of the surfactant content is 1.0% by mass or less, more preferably 0.9% by mass or less, and even more preferably 0.8% by mass or less.

[0125] [Other ingredients] The non-aqueous ink composition of this embodiment may also contain any known additives such as antioxidants or UV absorbers, light stabilizers, epoxides, polycarboxylic acids, surface conditioners, lubricants, leveling agents (acrylic or silicone), defoamers, pH adjusters, bactericides, preservatives, deodorizers, charge adjusters, and wetting agents as any component. Specific examples of antioxidants include hindered phenolic antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, and hydrazine antioxidants. Specifically, examples include BHA (2,3-butyl-4-hydroxyanisole) and BHT (2,6-di-tert-butyl-p-cresol). Furthermore, benzophenone compounds or benzotriazole compounds may be used as UV absorbers. Furthermore, specific examples of epoxides include: epoxide glycerol esters, epoxide fatty acid monoesters, and epoxide hexahydrophthalic acid esters, specifically: ADK CIZER O-130P and ADK CIZER O-180A (manufactured by ADEKA). Specific examples of polycarboxylic acids include: citric acid and maleic acid.

[0126] (Viscosity and surface tension of the ink composition) Regarding the inkjet ejection properties and ejection stability, the viscosity of the non-aqueous ink composition of this embodiment at 25°C is preferably 30 mPa·s or less, more preferably 20 mPa·s or less, and even more preferably 15 mPa·s or less. Furthermore, the viscosity of the non-aqueous ink composition of this embodiment is preferably 2.0 mPa·s or more, more preferably 3.0 mPa·s or more, and even more preferably 3.5 mPa·s or more.

[0127] Furthermore, regarding inkjet ejection performance, ejection stability, and leveling properties on the substrate, the surface tension of the non-aqueous ink composition of this embodiment is preferably 20 mN / m or more, more preferably 22 mN / m or more, and even more preferably 24 mN / m or more at 25°C. Also, the surface tension of the non-aqueous ink composition of this embodiment is preferably 40 mN / m or less, more preferably 37 mN / m or less, and even more preferably 35 mN / m or less.

[0128] ≪1-2. Non-aqueous ink composition of the second embodiment≫ The non-aqueous ink composition of this embodiment is ejected by inkjet printing and contains glossy pigments and organic solvents.

[0129] Furthermore, the organic solvent is characterized by containing the following organic solvent A.

[0130] Organic solvent A: selected from at least one of the group consisting of alkyl amide solvents (a1) and cyclic amide solvents (a2).

[0131] By using an organic solvent A (selected from at least one of the group consisting of alkyl amide solvents (a1) and cyclic amide solvents (a2)), even non-aqueous ink compositions containing glossy pigments can effectively remove clogging in the nozzles of the inkjet head and improve the cleanability and reversibility of the non-aqueous ink composition.

[0132] Furthermore, according to the inventors' understanding, although organic solvent A exhibits high drying properties on the substrate surface, it has low volatility within the plastic supply (e.g., a plastic tube). Therefore, non-aqueous ink compositions containing organic solvent A not only maintain clean-recovery properties but also yield recordings with excellent surface drying properties. The reason for the higher drying properties of organic solvent A on the substrate surface and the lower volatility within the plastic supply is that organic solvent A has low permeability through the plastic, and the boiling point of the organic solvent itself is not necessarily related to its volatility within the plastic supply.

[0133] Furthermore, when a glossy layer is formed from the non-aqueous ink composition of this embodiment containing organic solvent A (selected from at least one of alkyl amide solvents (a1) and cyclic amide solvents (a2)), the gloss of the glossy layer can be enhanced, and a good metallic gloss is imparted.

[0134] Furthermore, the water content in the non-aqueous ink composition of this embodiment is preferably 5.0% by mass or less, more preferably 1.0% by mass or less, and even more preferably 0.5% by mass or less. If moisture originating from raw materials or from atmospheric moisture during the manufacturing process is introduced, the storage stability or ejection stability of the non-aqueous ink composition may deteriorate, or solid substances may be generated due to the components contained in the non-aqueous ink composition. By reducing the water content in the non-aqueous ink composition to make it as water-free as possible (without intentionally making it contain water), storage stability and cleanability can be improved more effectively.

[0135] The components contained in the non-aqueous ink composition of this embodiment will be described below.

[0136] [Organic solvents] Organic solvents can disperse or dissolve the components contained in the non-aqueous ink composition of this embodiment. The organic solvent contains organic solvent A (selected from at least one of the group consisting of alkyl amide solvents (a1) and cyclic amide solvents (a2)).

[0137] The preferred solvents among the alkyl amide solvents (a1) and cyclic amide solvents (a2) are the same in type and range of content as those in the non-aqueous ink composition of the first embodiment described above.

[0138] Of the organic solvents A, it is more preferably "a solvent containing an alkyl amide (a1)". If it is "a solvent containing an alkyl amide (a1)", it combines cleanability and surface drying on the substrate, and has good component compatibility with the inkjet recording device. The effects of the present invention are fully realized by including at least one of an alkyl amide solvent (a1) and a cyclic amide solvent (a2) in organic solvent A, but two or more solvents of organic solvent A can also be mixed. By mixing two or more, the balance of storage stability, component compatibility, surface drying, and cleanability can be adjusted arbitrarily. When two or more organic solvents A are mixed, the preferred range of the total content of organic solvent A in the non-aqueous ink composition is the same as that of the non-aqueous ink composition of the first embodiment described above.

[0139] (4) Other organic solvents The non-aqueous ink composition of this embodiment may also contain organic solvents other than organic solvent A mentioned above. Specifically, examples include: dialkyl ethers of glycols with alkyl-substituted OH groups at both ends, monoalkyl ethers of glycols with alkyl-substituted OH groups at one end, carbonates, acetate solvents, cyclic esters, etc.

[0140] The preferred type of solvent for the glycol ether solvent is the same as that for the glycol ether solvent in the non-aqueous ink composition of the first embodiment described above.

[0141] Furthermore, similar to the non-aqueous ink composition of the first embodiment described above, it is preferable to combine two or more glycol ether solvents with different flash points. Similar to the non-aqueous ink composition of the first embodiment described above, this results in a non-aqueous ink composition that effectively combines high cleanability and surface drying properties on the substrate, thus demonstrating the effects of the present invention.

[0142] Furthermore, as other solvents besides glycol ether solvents, acetate solvents represented by formulas (2-3) can be cited as examples. By using acetate solvents, glossy pigments can be effectively dispersed, thereby improving the storage stability of non-aqueous ink compositions containing glossy pigments. [Chemistry 6] (In formula (2-3), X1 is an alkyl group, and X2 is a hydrogen or alkyl group. n represents an integer from 1 to 4.)

[0143] Examples of acetate ester solvents include: 3-methoxybutyl acetate, 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, 1-methoxy-2-propyl acetate, 2-methylbutyl acetate, 3-methoxybutyl ether acetate, cyclohexyl acetate, and other acetate ester solvents.

[0144] There is no particular limitation on the content of the acetate-based solvent, but the lower limit of the acetate-based solvent content is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more. This further improves the storage stability of the non-aqueous ink composition containing glossy pigments. The upper limit of the acetate-based solvent content is preferably 10.0% by mass or less, more preferably 7.0% by mass or less, and even more preferably 5.0% by mass or less. This allows for a relatively increased content of other components such as organic solvent A, thus creating a non-aqueous ink composition that combines high cleanability and surface drying properties on the substrate.

[0145] Furthermore, it may also contain solvents other than glycol ether solvents or acetate solvents. Specifically, examples of "solvents other than glycol ether solvents" exemplified in the non-aqueous ink composition of the first embodiment described above can be cited. Preferably, it contains at least one selected from the group consisting of glycol ether solvents, acetate solvents, cyclic esters, carbonates, diesters, lactates, amides, and alcohols. The preferred range of the total content of other organic solvents contained in the non-aqueous ink composition is the same as that in the non-aqueous ink composition of the first embodiment described above.

[0146] [Glossy Pigments] The non-aqueous ink composition of this embodiment contains a glossy pigment. The glossy pigment has the function of imparting a metallic sheen to the printed surface. Examples of glossy pigments include those containing pearlescent pigments or metallic glossy pigments. Preferably, the glossy pigment contains a metallic glossy pigment. This allows for the imparting of a better metallic sheen to the printed surface.

[0147] Furthermore, when the glossy pigment contains metallic glossy pigments, the content of metallic glossy pigments is preferably 30% or more by mass of the total glossy pigment, more preferably 50% or more by mass, and even more preferably 70% or more by mass.

[0148] Examples of pearlescent pigments include: mica, titanium dioxide-coated mica, fish scale foil, bismuth oxychloride, silicon dioxide, metal oxides, and their layers, which possess a pearly or interference luster.

[0149] Examples of metallic glossy pigments include: elemental metals such as aluminum, silver, gold, nickel, chromium, tin, zinc, indium, titanium, and copper; metal compounds; alloys; and mixtures thereof. Preferably, a metallic glossy pigment is one comprising at least one selected from the group consisting of aluminum, aluminum alloys, indium, indium alloys, nickel, and nickel alloys, and more preferably one comprising at least aluminum or aluminum alloys. By using a metallic glossy pigment comprising at least one selected from the group consisting of aluminum, aluminum alloys, indium, indium alloys, nickel, and nickel alloys, a better metallic luster can be imparted to the printed surface.

[0150] There is no particular limitation on the lower limit of the content of glossy pigment, but it is preferably 0.5% by mass or more, more preferably 0.8% by mass or more, more preferably 1.0% by mass or more, and even more preferably 1.2% by mass or more of the total amount of the non-aqueous ink composition. This allows for the imparting of a better metallic gloss to the printed surface. In particular, a higher content of glossy pigment results in a more glossy print, but there is a tendency for clogging to occur in the inkjet head nozzles, further reducing cleanability and reversibility. However, by containing organic solvent A (selected from at least one of the group consisting of alkylamide solvents (a1) and cyclic amide solvents (a2)), even non-aqueous ink compositions containing a higher content of glossy pigment can effectively remove clogging from the inkjet head nozzles and improve the cleanability and reversibility of the non-aqueous ink composition.

[0151] There is no particular upper limit to the content of glossy pigments, but it is preferably less than 10.0% by mass of the total amount of the non-aqueous ink composition, more preferably less than 8.0% by mass, and even more preferably less than 6.0% by mass. This can improve the cleanability and reversibility of the non-aqueous ink composition.

[0152] There is no particular limitation on the lower limit of the volumetric cumulative 50% particle size (D50) of the metallic glossy pigment, but it is preferably 0.01 μm or more, more preferably 0.05 μm or more, further preferably 0.10 μm or more, and even more preferably 0.50 μm or more. By ensuring that the volumetric cumulative 50% particle size (D50) of the metallic glossy pigment is 0.01 μm or more, when a glossy layer is formed from the non-aqueous ink composition of this embodiment, the gloss of the glossy layer can be improved, and a good metallic gloss is imparted.

[0153] There is no particular limit to the upper limit of the volumetric cumulative 50% particle size (D50) of glossy pigments, but it is preferably below 5.0 μm, more preferably below 3.0 μm, and even more preferably below 2.5 μm. By ensuring that the volumetric cumulative 50% particle size (D50) of metallic glossy pigments is below 5.0 μm, clogging in the inkjet nozzle can be effectively cleared, improving the ejection stability and cleanability of non-aqueous ink compositions.

[0154] In particular, the non-aqueous ink composition of this embodiment, by containing organic solvent A (selected from at least one of the group consisting of alkyl amide solvents (a1) and cyclic amide solvents (a2), can effectively remove clogging in the nozzle of the inkjet head and improve the cleanliness and reversibility of the non-aqueous ink composition. Therefore, even if the volume-based cumulative particle size (D50) of the glossy pigment is increased by 50%, the decrease in the ejection stability or cleanliness and reversibility of the non-aqueous ink composition can be suppressed. Furthermore, by increasing the volume-based cumulative particle size (D50) of the glossy pigment by 50%, when a glossy layer is formed from the non-aqueous ink composition of this embodiment, the gloss of the glossy layer can be improved, giving it a good metallic gloss.

[0155] Furthermore, in this specification, the term "cumulative 50% particle size (D50)" refers to the particle size at which the cumulative volume, calculated from the smallest diameter side, reaches 50%. "Cumulative 50% particle size (D50)" is sometimes also referred to as "volume average particle size D50" or "median particle size".

[0156] There is no particular limit to the upper limit of the volumetric cumulative 90% particle size (D90) of metallic glossy pigments, but it is preferably below 10.0 μm, more preferably below 7.0 μm, and even more preferably below 5.0 μm.

[0157] Furthermore, in this specification, the term "cumulative 90% particle size based on volume (D90)" refers to the particle size at which the cumulative volume, calculated from the smaller diameter side, reaches 90%.

[0158] Metallic glossy pigments are preferably composed of particles with flat surfaces. Flat surfaces allow for the creation of a glossy layer with higher gloss. Examples of particles with flat surfaces include cubic or cuboid particles, as well as flat or scaly particles. This allows for the application of a better metallic sheen to the printed material. Furthermore, flat or scaly particles are more preferably flat.

[0159] At this point, the lower limit of the thickness of the metallic glossy pigment is preferably 5 nm or more, more preferably 10 nm or more, and even more preferably 15 nm or more. The upper limit of the thickness of the metallic glossy pigment is preferably 5.0 μm or less, more preferably 3.0 μm or less, and even more preferably 1.0 μm or less.

[0160] Furthermore, the volumetric cumulative 50% particle size (D50), volumetric cumulative 90% particle size (D90), and thickness of glossy pigments can be measured using instruments such as the "FPIA-3000S" manufactured by Sysmex Corporation and the "SALD 7500nano" laser diffraction particle size analyzer manufactured by Shimadzu Corporation.

[0161] Glossy pigments can be obtained by mechanically shaping metal-containing particles, for example, by grinding them in a ball mill or atrium mill. Metal-containing particles can also be obtained by well-known atomization methods.

[0162] Furthermore, as another method for manufacturing glossy pigments, the metal-containing thin film formed on a substrate can be micronized. An example of such a method is as follows: a metal-containing thin film of approximately 5.0 nm to 5.0 μm is formed on a flat substrate coated with a release resin layer by vacuum evaporation, ion plating, or sputtering; the metal-containing thin film is then peeled off from the substrate and micronized. Furthermore, the term "metal-containing thin film" is used to include thin films containing metal compounds such as metal oxides. The lower limit of the thickness of the metal-containing thin film is preferably 5 nm or more, more preferably 10 nm or more, and even more preferably 15 nm or more. The upper limit of the thickness of the metal-containing thin film is preferably 5.0 μm or less, more preferably 3.0 μm or less, and even more preferably 1.0 μm or less.

[0163] Specific examples of substrates used in the manufacture of glossy pigments include polytetrafluoroethylene films; polyethylene films; polypropylene films; polyester films such as polyethylene terephthalate; polyamide films such as 66 nylon and 6 nylon; polycarbonate films; triacetate films; and polyimide films. Preferred substrates are films made of polyethylene terephthalate or copolymers thereof.

[0164] There is no particular limitation on the lower limit of the preferred thickness of the substrate used for manufacturing glossy pigments, but it is preferably 10 μm or more, more preferably 15 μm or more, and even more preferably 20 μm or more. A substrate thickness of 10 μm or more ensures good workability. There is no particular limitation on the upper limit of the preferred thickness of the sheet-like substrate, but it is preferably 150 μm or less, more preferably 145 μm or less, and even more preferably 140 μm or less. A substrate thickness of 150 μm or less improves the flexibility of the obtained laminate, making it easier to roll or peel.

[0165] Specific examples of resins used in the release resin layer coated on the substrate include polyvinyl alcohol, polyvinyl butyral, polyethylene glycol, polyacrylic acid, polyacrylamide, cellulose derivatives, polyvinyl acetal, acrylic copolymers, and modified nylon resins. When preparing the release resin layer, the resin solution is applied to the sheet substrate using coating methods such as gravure coating, roller coating, blade coating, extrusion coating, dip coating, and spin coating to form the release resin layer.

[0166] The lower limit of the thickness of the release resin layer is not particularly limited, but it is preferably 0.1 μm or more, more preferably 0.3 μm or more, and even more preferably 0.5 μm or more. With a thickness of 0.1 μm or more, the metal-containing film can be easily peeled off from the substrate. The upper limit of the thickness of the release resin layer is not particularly limited, but it is preferably 50 μm or less, more preferably 30 μm or less, and even more preferably 10 μm or less. With a thickness of 50 μm or less, the metal-containing film can be easily peeled off from the substrate.

[0167] Furthermore, non-aqueous ink compositions or dispersions for non-aqueous ink compositions can be manufactured from substrates on which metal-containing films are formed. This can be achieved by immersion in a solvent capable of dissolving the release resin without reacting with the glossy pigment, or by simultaneous ultrasonic treatment during immersion. Examples of such solvents include organic solvents constituting the non-aqueous ink composition. The release resin functions as a dispersant for the glossy pigment, thereby improving its dispersibility. In this case, the particle size and film thickness of the glossy pigment can be adjusted by the conditions during the formation of the metal-containing film or by the ultrasonic dispersion time. Alternatively, the glossy pigment can be separated from the release resin solution by centrifugation, recovered, and dispersed in the organic solvent constituting the non-aqueous ink composition. Furthermore, the glossy pigment can also be surface-treated with silane compounds, fluorinated compounds, phosphoric acid, phosphate esters, fatty acids, fatty acid esters, etc.

[0168] Furthermore, the non-water-based ink composition of this embodiment may also contain colorants other than glossy pigments.

[0169] [Pigment Dispersant] Dispersants may also be used in the non-aqueous ink composition of this embodiment, if necessary. The preferred type of pigment dispersant is the same as that in the non-aqueous ink composition of the first embodiment described above. The preferred range of the content of pigment dispersant in the non-aqueous ink composition is the same as that in the non-aqueous ink composition of the first embodiment described above.

[0170] [Resin] The non-aqueous ink composition of this embodiment may or may not contain resin. By containing resin, the fixation, water resistance, and elongation of the recording layer formed from the non-aqueous ink composition can be improved. Furthermore, the gloss of the obtained recorded material can be improved. The preferred type of resin is the same as that 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 that in the non-aqueous ink composition of the first embodiment described above.

[0171] [Surfactants] A surfactant may also be added to the non-aqueous ink composition of this embodiment. The preferred type of surfactant is the same as that used in the non-aqueous ink composition of the first embodiment described above. The preferred range of surfactant content in the non-aqueous ink composition is the same as that in the non-aqueous ink composition of the first embodiment described above.

[0172] [wax] Wax can also be added to the non-aqueous ink composition of this embodiment. This imparts smoothness to the surface of the glossy layer formed from the non-aqueous ink composition of this embodiment, thereby improving the abrasion resistance of the obtained printed material.

[0173] Here, "wax" refers to organic substances or silicone compounds that are solid at or below room temperature but liquefy upon heating. Specifically, examples include: low molecular weight polyolefin waxes such as polyethylene, polypropylene, polybutene, polyethylene mixed waxes, polypropylene waxes, and polypropylene mixed waxes; silicones with softening points; silicone-acrylic waxes; fatty acid amides such as oleic acid amides, erucic acid amides, ricinoleic acid amides, and stearic acid amides; plant-based waxes such as ester waxes, carnauba wax, rice bran wax, candelilla wax, wood wax, and jojoba oil; animal-based waxes such as beeswax, lanolin, and cetearyl wax; mineral-based waxes such as lignite wax, ozokerite, ceresin, and Fischer-Tropsch wax; petroleum-based waxes such as paraffin wax, microcrystalline wax, paraffin grease, and mixed paraffin waxes; and modified forms of these waxes. Commercially available products of these waxes are readily available. In the non-aqueous ink composition of this embodiment, a single type of wax can be used, or two or more types of wax can be used in combination.

[0174] The wax contained in the non-aqueous ink composition of this embodiment can also be liquid at room temperature, and its melting point is not particularly limited. The lower limit of the melting point is preferably above 20°C, more preferably above 25°C, and even more preferably above 30°C. By ensuring the wax's melting point is above 20°C, the occurrence of wax melting and surface stickiness, as well as the adhesion of printed materials, can be suppressed. The upper limit of the melting point is preferably below 130°C, more preferably below 125°C, and even more preferably below 120°C. By ensuring the wax's melting point is below 130°C, the whitening of the printed material can be suppressed, and a better metallic gloss can be imparted to the printed surface.

[0175] In the non-aqueous ink composition of this embodiment, there is no particular limitation on the lower limit of the wax content, but it is preferably 0.05% by mass or more, more preferably 0.07% by mass or more, and even more preferably 0.1% by mass or more. This allows for better surface smoothness of the printed material, resulting in printed matter with good abrasion resistance. The upper limit of the wax content is preferably 1.0% by mass or less, more preferably 0.8% by mass or less, and even more preferably 0.5% by mass or less. This allows for better metallic gloss of the printed material.

[0176] [Other ingredients] The non-aqueous ink composition of this embodiment may also contain other components as arbitrary 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.

[0177] (Viscosity and surface tension of non-aqueous ink compositions) The preferred viscosity and preferred surface tension range of the non-aqueous ink composition of this embodiment are the same as those of the non-aqueous ink composition of the first embodiment described above.

[0178] ≪2. Method for manufacturing ink composition≫ As a method for manufacturing the ink composition according to this embodiment, it can be manufactured by mixing an organic solvent A (selected from at least one of the group consisting of alkyl amide solvents (a1) and cyclic amide solvents (a2), a white pigment or a glossy pigment, and other components (e.g., resin, etc.) as needed, using a coating shaker. At this time, zirconia beads can also be used to disperse the components. Furthermore, if necessary, the obtained non-aqueous ink composition can be subjected to degassing treatment to adjust the dissolved oxygen or dissolved nitrogen content to the desired value.

[0179] In this case, it is preferable to pre-dry the organic solvent. By pre-drying the organic solvent, the water content in the non-aqueous ink composition can be reduced. Examples of methods for drying the organic solvent include: blowing a drying inert gas (e.g., nitrogen) for a specific time in an inert gas atmosphere such as nitrogen; or purifying the organic solvent by distillation; or passing the organic solvent through a semi-permeable membrane that is selectively permeable to water; or selectively adsorbing water mixed in the organic solvent with a water-absorbing agent.

[0180] ≪3. Ink Set≫ The ink set of this embodiment contains a plurality of ink compositions comprising the above-described non-aqueous ink composition. The non-aqueous ink compositions of the first and second embodiments described above can combine high cleanability and surface drying properties on the substrate, and even in the ink set of this embodiment, a record with excellent surface drying properties can be obtained.

[0181] Examples of ink compositions other than the non-aqueous ink composition containing white pigment in the first embodiment described above include: black ink compositions containing black pigment, or colored ink compositions such as yellow, magenta, cyan, light magenta, light cyan, light black, orange, green, and red, or glossy ink compositions containing glossy pigments, or transparent ink compositions without colorants.

[0182] For example, by using the non-aqueous ink composition containing white pigment of the first embodiment described above as a non-aqueous ink composition for forming the underlayer or surface layer, the concealment of the obtained record can be improved. Furthermore, for example, by using a colored ink composition other than the non-aqueous ink composition containing white pigment of the first embodiment described above, the desired image can be formed.

[0183] Alternatively, at least one of the group consisting of black ink composition, colored ink composition, glossy ink composition and transparent ink composition may be simultaneously sprayed onto the surface of the substrate by inkjet printing along with the non-aqueous ink composition containing white pigment of the first embodiment described above.

[0184] Furthermore, examples of ink compositions other than the non-aqueous ink composition containing glossy pigments in the second embodiment described above include: black ink compositions containing black pigments, or colored ink compositions such as yellow, magenta, cyan, light magenta, light cyan, light black, white, orange, green, and red, and transparent ink compositions without colorants.

[0185] For example, by using the non-aqueous ink composition containing glossy pigments of the second embodiment described above as a non-aqueous ink composition for forming the underlayer or surface layer, the gloss of the obtained record can be improved. Furthermore, for example, by using a colored ink composition as an ink composition other than the non-aqueous ink composition containing glossy pigments, the desired image can be formed.

[0186] Alternatively, at least one of the group consisting of black ink composition, colored ink composition, white ink composition and transparent ink composition may be simultaneously sprayed onto the surface of the substrate by inkjet printing along with the non-aqueous ink composition containing glossy pigment of the second embodiment described above.

[0187] ≪4. Recording Method Using Ink Compositions≫ The recording method of this embodiment is a recording method in which the non-aqueous ink composition of the first and second embodiments described above is sprayed onto the surface of a substrate by inkjet printing. The non-aqueous ink composition of the first and second embodiments described above can combine high cleanability and surface drying properties on the substrate, and the recording method of this embodiment can also obtain a recorded object with excellent surface drying properties.

[0188] In particular, the non-aqueous ink compositions of the first and second embodiments described above exhibit excellent surface drying properties, enabling high-speed transport of the substrate (recording medium) and inkjet spraying onto the surface of the substrate, thereby increasing the manufacturing speed of printed materials. The same applies to the method for manufacturing printed materials described later.

[0189] Specifically, the recording speed (substrate conveying speed) in the recording method of this embodiment varies depending on the type of substrate, preferably 10 m² / h or more, more preferably 20 m² / h or more, and even more preferably 30 m² / h or more.

[0190] The inkjet recording apparatus that ejects the non-aqueous ink compositions of the first and second embodiments described above by inkjet printing can be any previously known device. For example, an inkjet printer such as the VersaArt RE-640 (manufactured by Roland DG Inc.) can be used.

[0191] As one example of the configuration of an inkjet recording device, an inkjet recording device that is an on-carriage type and a serial printer type will be described. The inkjet recording device that can implement the recording method of this embodiment can also be an off-carriage type inkjet recording device in which the ink cartridge is fixed to the outside, or an inkjet recording device that is a row printer type in which the inkjet head does not move and sprays the ink composition onto the recording medium (substrate).

[0192] Furthermore, the inkjet recording device is preferably equipped with a heating mechanism and a fixing mechanism for fixing the substrate. By using the heating mechanism of the inkjet recording device to control the surface temperature of the substrate, the non-aqueous ink composition sprayed onto the substrate (recording medium) dries, thereby allowing the organic solvents contained in the non-aqueous ink composition to evaporate.

[0193] Furthermore, by using a fixing mechanism to fix the substrate, the non-aqueous ink composition can be dried while the substrate (recording medium) is fixed, thus suppressing uneven heating caused by bending of the substrate due to heating. This allows for effective drying of the non-aqueous ink composition sprayed onto the substrate (recording medium). This drying and fixing mechanism is particularly effective when high-speed transport of the substrate (recording medium) is used to increase the manufacturing speed of recorded materials.

[0194] The heating mechanism of an inkjet recording device can be a preheater, a platen heater, an afterheater, or a mechanism that blows warm air onto the recorded material. Furthermore, multiple such heating mechanisms can be combined.

[0195] There are no particular limitations on the surface temperature of the substrate heated by the heating mechanism, as long as it is sufficient to evaporate the organic solvent contained in the non-aqueous ink composition. The lower limit of the surface temperature of the substrate 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 surface temperature of the substrate is preferably 70°C or lower, more preferably 60°C or lower, and even more preferably 50°C or lower.

[0196] The inkjet method can be either piezoelectric, which uses piezoelectric elements, or thermal, which uses heating elements; there are no particular limitations.

[0197] Furthermore, the non-aqueous ink compositions of the first and second embodiments described above have high drying properties, therefore the aforementioned mechanism is not necessarily required in the inkjet recording apparatus of this embodiment. For example, the heating mechanism can be omitted from the inkjet recording apparatus to miniaturize the device and shorten the overall conveying section, thereby increasing the printing speed.

[0198] Furthermore, the inkjet recording device can be configured as follows: it has a supply tube that connects a container (ink cartridge or ink bottle, etc.) storing the non-aqueous ink composition of the first and second embodiments to an inkjet head that ejects the non-aqueous ink composition of the first and second embodiments, and the non-aqueous ink composition of the first and second embodiments is supplied to the inkjet head through the supply tube and ejected by inkjet method.

[0199] When the organic solvent A (selected from at least one of the group consisting of alkyl amide solvents (a1) and cyclic amide solvents (a2)) contained in the non-aqueous ink compositions of the first and second embodiments is present in the supply tube, its evaporation rate is relatively lower than that of other organic solvents. Therefore, inkjet printing can be performed while maintaining the amount of organic solvent contained in the non-aqueous ink composition. This effectively removes clogging from the nozzles of the inkjet head and improves the cleanliness and reversibility of the non-aqueous ink composition.

[0200] There are no particular limitations on the material of the supply pipe, but examples include: polyethylene resin and other polyolefin resins, ethylene propylene diene rubber, nylon, polyurethane, PTFE, etc. Among these, polyethylene resin and ethylene propylene diene rubber are preferred.

[0201] Furthermore, in the inkjet recording apparatus of this embodiment, the non-aqueous ink composition containing white pigment of the first embodiment or the non-aqueous ink composition containing glossy pigment of the second embodiment can be used. Simultaneously, inks of various colors such as yellow, magenta, cyan, black, or light magenta, light cyan, light black, orange, green, and red can also be used. There are no particular limitations on the printing order of the colors, or the position or configuration of the inkjet head. Furthermore, the inkjet recording apparatus of this embodiment may or may not have a take-up mechanism for the recording medium (substrate), a drying mechanism for drying the surface of the substrate, or an ink circulation mechanism.

[0202] ≪5. Methods of Manufacturing Records≫ The recording method using the non-aqueous ink composition of the first and second embodiments described above can also be defined as a method for manufacturing a record. The non-aqueous ink composition of the first and second embodiments described above can combine high cleanability and surface drying properties on the substrate, and even in the method for manufacturing a record in this embodiment, a record with excellent surface drying properties can be obtained.

[0203] ≪6. Records≫ The layers constituting the recording object manufactured by the recording object manufacturing method of the above-described embodiments will be described. Furthermore, the recording object in this embodiment is formed by forming a white layer of the non-aqueous ink composition of the first embodiment and / or a glossy layer of the non-aqueous ink composition of the second embodiment on the surface of a substrate. However, the non-aqueous ink composition of the first embodiment is not limited to forming a white layer, and the non-aqueous ink composition of the second embodiment is not limited to forming a glossy layer. For example, a recording layer can also be formed by simultaneously spraying the non-aqueous ink composition containing white pigment of the first embodiment with colored ink compositions such as yellow, magenta, cyan, black, light magenta, light cyan, light black, orange, green, and red, thereby forming the desired image. Alternatively, the non-aqueous ink composition containing glossy pigment of the second embodiment can also be simultaneously sprayed with colored ink compositions such as yellow, magenta, cyan, black, light magenta, light cyan, light black, orange, green, red, and white, thereby forming the desired image. Furthermore, the phrase "simultaneously ejecting the aforementioned non-aqueous ink composition containing white pigment and the colored ink composition" does not mean that these multiple ink compositions are ejected onto the surface of the substrate at an absolutely simultaneous time using an inkjet method. Rather, it means that multiple ink compositions are ejected at approximately the same time to form the desired image, as is the case with conventional inkjet methods (including tandem head methods, row-and-column head methods, etc.). Similarly, the phrase "simultaneously ejecting the aforementioned non-aqueous ink composition containing glossy pigment and the colored ink composition" does not mean that these multiple ink compositions are ejected onto the surface of the substrate at an absolutely simultaneous time using an inkjet method. Rather, it means that multiple ink compositions are ejected at approximately the same time to form the desired image, as is the case with conventional inkjet methods (including tandem head methods, row-and-column head methods, etc.).

[0204] [Media (Recorded Media)] There are no particular limitations on the substrate (recording medium) that can be used in the recording method of this embodiment. Various substrates can be used, including non-absorbent substrates such as resin substrates, metal plates, and glass, absorbent substrates such as paper or cloth, and substrates with an absorbing layer or other substrates that have undergone surface coating treatment.

[0205] Of these, since the non-aqueous ink compositions of the first and second embodiments described above are water-free non-aqueous ink compositions, it is preferable that the surface mainly comprises resin. In particular, the non-aqueous ink compositions of the first and second embodiments described above contain an organic solvent A (selected from at least one of the group consisting of alkyl amide solvents (a1) and cyclic amide solvents (a2)) that exhibits permeability to resin substrates, thus resulting in less ink bleeding on the resin-containing medium (recording medium). Examples of resins include: polyvinyl chloride polymers or acrylic resins, PET, polycarbonate, PE, PP, etc. It can also be used for resin substrates such as those for which a film is laminated to the recording surface of the recording material (so-called lamination resin substrates). It is particularly preferred that the surface of the recording medium comprises a rigid or flexible polyvinyl chloride polymer. Examples of substrates (recording media) comprising a polyvinyl chloride polymer are polyvinyl chloride materials (films or sheets).

[0206] [White layer] The white layer is formed by evaporating the solvent contained in the non-aqueous ink composition containing white pigment of the first embodiment described above. Even when containing a large amount of white pigment, the non-aqueous ink composition containing white pigment of the first embodiment can effectively clear clogging in the inkjet head nozzles, improving the cleanliness and reversibility of the non-aqueous ink composition. Furthermore, the non-aqueous ink composition containing white pigment of the first embodiment has high surface drying properties on the substrate; even if the amount of non-aqueous ink composition ejected is increased to impart excellent concealment, the drying time is not excessive. Therefore, using the non-aqueous ink composition containing white pigment of the first embodiment, for example, it is easy to control the white pigment content or the amount of non-aqueous ink composition ejected, and a white layer with high concealment is easily formed. This white layer can be the bottom or top layer of the recording layer described later, or it can be the same layer as the recording layer described later.

[0207] [Glossy layer] The glossy layer is formed by evaporating the solvent contained in the non-aqueous ink composition containing glossy pigments of the second embodiment described above. Even when containing a large amount of glossy pigments, the non-aqueous ink composition containing glossy pigments of the second embodiment can effectively clear clogging within the inkjet head nozzles, improving the cleanliness and reversibility of the non-aqueous ink composition. Furthermore, the non-aqueous ink composition containing glossy pigments of the second embodiment exhibits high surface drying properties on the substrate; even if the ejection volume of the non-aqueous ink composition is increased to impart excellent concealment, the drying time is not excessive. Therefore, using the non-aqueous ink composition containing glossy pigments of the second embodiment, it is easy to control, for example, the content of glossy pigments or the ejection volume of the non-aqueous ink composition, easily forming a glossy layer with high gloss. This glossy layer can be the bottom or top layer of the recording layer described later, or it can be the same layer as the recording layer described later.

[0208] [Record Layer] The term "recording layer" refers to the layer on which the desired image is formed by a combination of inks such as yellow, magenta, cyan, black, light magenta, light cyan, light black, orange, green, and red. The non-aqueous ink composition containing white pigment in the first embodiment, which forms the white layer, or the non-aqueous ink composition containing glossy pigment in the second embodiment, which forms the glossy layer, exhibits higher surface drying properties on the substrate, thus increasing the printing speed.

[0209] [Other layers] The recording medium of this embodiment can further have a layer with the desired function on the medium (recording medium) or the entire surface of the recording medium. For example, an undercoat layer can be formed to improve the adhesion between the medium (recording medium) and the glossy layer or recording layer, and a glossy layer containing glossy pigments or a white layer containing white pigments can be formed as the underlayer. Furthermore, such glossy layers or white layers can be formed from the non-aqueous ink compositions of the first and second embodiments described above, or they can be formed without the non-aqueous ink compositions of the first and second embodiments described above. In addition, in order to further impart abrasion resistance or gloss to the recording medium, an outer coating layer containing at least one of resin and wax can be formed on the entire surface of the recording medium. Furthermore, by including fillers or varying the film thickness in pixel units, a layer with an uneven texture (matte surface) can be formed on the entire surface of the recording medium. Furthermore, in order to impart weather resistance to the recorded material, a weather-resistant layer containing ultraviolet absorbers or light stabilizers, a glossy layer containing glossy pigments, or a white layer containing white pigments can be formed on the surface of the entire recorded material. Moreover, these glossy layers or white layers can be formed from the non-aqueous ink compositions of the first and second embodiments described above, or they may not be formed from the non-aqueous ink compositions of the first and second embodiments described above. [Example]

[0210] The present invention will be described in more detail below by way of examples, but the present invention is not limited to any of the descriptions.

[0211] (First Implementation) 1. Resin Production (1) Acrylic resin A mixture of 150 g of methyl methacrylate, 50 g of butyl methacrylate, and a specific amount of tributyl peroxide (2-ethylhexanoate) (polymerization initiator) was added dropwise over 1.5 hours to 300 g of diethylene glycol diethyl ether at 100°C. After the addition was complete, the mixture was reacted at 100°C for 2 hours and then cooled to obtain a colorless and transparent polymer solution of methyl methacrylate. Subsequently, the solvent was thoroughly removed from the polymer solution by distillation to obtain the polymer of methyl methacrylate. By varying the amount of tributyl peroxide (2-ethylhexanoate) used as the polymerization initiator, the average molecular weight of the polymerized methyl methacrylate (acrylic resin) was controlled to be 10,000~105,000 (the mass of the polymerization initiator used at this time is recorded in Table 1 below. Table 1 is labeled "starting dose").

[0212] (2) Vinyl chloride-vinyl acetate copolymer resin In a high-pressure reactor equipped with a stirring device, after nitrogen purging, 100 parts by weight of deionized water, 40 parts by weight of methanol, 32 parts by weight of vinyl chloride, 5 parts by weight of vinyl acetate, 0.2 parts by weight of glycidyl methacrylate, 3.55 parts by weight of hydroxypropyl acrylate, 0.1 parts by weight of hydroxypropyl methylcellulose (suspending agent), 0.026 parts by weight of di(2-ethylhexyl) peroxide dicarbonate (polymerization initiator), and a specific amount of di-3,5,5-trimethylhexanol peroxide (polymerization initiator) were added. Under a nitrogen atmosphere, the mixture was stirred and heated to 63°C. Immediately after reaching 63°C, 48 parts by weight of vinyl chloride were continuously injected over a period of 6 hours, followed by a 5.4-hour injection of a mixture of 0.6 parts by weight of glycidyl methacrylate and 10.65 parts by weight of hydroxypropyl acrylate to initiate a copolymerization reaction. When the pressure inside the high-pressure reactor reached 0.3 MPa, the residual pressure was released, and the resin slurry was cooled, filtered, and dried to obtain a vinyl chloride-based copolymer resin. By changing the amount of di-3,5,5-trimethylhexanol peroxide used as the polymerization initiator, the average molecular weight of the vinyl chloride-vinyl acetate copolymer resin was controlled to be 40,000 to 90,000 (the mass of the polymerization initiator used at this time is recorded in Table 1 below. Table 1 is denoted as "starting dose").

[0213] [Table 1] Weight average molecular weight (Relative molecular mass) Starting dose (g) acrylic resin Synthetic resin ① Mw=10000 4.50 Synthetic resin ② Mw=15000 3.30 Synthetic resin ③ Mw=30000 1.20 Synthetic resin ④ Mw=80000 0.20 Synthetic resin ⑤ Mw=105000 0.10 Vinyl chloride-vinyl acetate copolymer resin Synthetic resin ① Mw=40000 0.58 Synthetic resin ② Mw=50000 0.37 Synthetic resin ③ Mw=75000 0.14 Synthetic resin ④ Mw=90000 0.06

[0214] (3) 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 added to a round-bottom flask. The mixture was slowly heated to 240°C over 4 hours, while the distillate was discharged from the system and the esterification reaction was carried out. After the esterification reaction was completed, the pressure was reduced to 10 mmHg over 30 minutes, and the temperature was raised to 250°C for initial polymerization. Subsequently, secondary polymerization was carried out at a pressure below 1 mmHg for 1 hour to obtain a polyester resin.

[0215] (4) Polyurethane resin 192.5 parts by weight of polycarbonate diol (PLACCEL CD-220: manufactured by Daicel), 41.6 parts by weight of isophorone diisocyanate (IPDI: manufactured by Evonik), and 100 parts by weight of N,N-diethylmethylamine (DEF) were added to a round-bottom flask and mixed evenly. Then, a mixture of 0.01 parts by weight of T100BHJ (catalyst) and 0.09 parts by weight of N,N-diethylmethylamine (DEF) was added and reacted at 75°C for 3 hours to obtain a prepolymer with isocyanate groups at the ends. 250 parts by weight of N,N-diethylmethylformamide (DEF) were added and dissolved uniformly. Then, a chain elongating agent solution prepared by dissolving 12 parts by weight of 3-aminomethyl-3,5,5-trimethylcyclohexylamine (IPD: manufactured by Evonik) in 100 parts by weight of N,N-diethylmethylformamide (DEF) was added, and the mixture was stirred at 60°C for 40 minutes. Subsequently, a reaction terminator prepared by dissolving 3.8 parts by weight of monoisopropanolamine (MIPA: manufactured by Daicel) in 50 parts by weight of N,N-diethylmethylformamide was added. Finally, 250 parts by weight of N,N-diethylmethylformamide (DEF) was added to obtain a polyurethane solution with a solid content of 25.0%.

[0216] 2. Manufacturing of non-water-based ink compositions The non-aqueous ink compositions of the examples and comparative examples were prepared according to the ratios and composition shown in the table below, using various organic solvents, resins, dispersants, and pigments. Specifically, the non-aqueous ink compositions were prepared by dispersing the components using zirconia beads in a paint shaker. Units are percentages by mass.

[0217] 3. Evaluation (Spreading properties) The blurring properties of the non-aqueous ink compositions of the Examples and Comparative Examples were evaluated. Specifically, using an inkjet printer (trade name VersaArt RE-640, manufactured by Roland DG Inc.), the non-aqueous ink compositions of the Examples and Comparative Examples were printed using inkjet printing in a high-quality printing mode (1440×720dpi) at a substrate surface temperature of 40°C on a recording medium (polyvinyl chloride tape (IMAGin JT5829R: manufactured by MACtac)). The printed material was dried in an oven at 60°C for 5 minutes, and the blurring properties of the printed material were observed under a visual magnifying glass (×10) (referred to as "blurring properties" in the table). Evaluation Criteria Evaluation 5: No ink spreading was observed under a magnifying glass. Evaluation 4: No ink bleeding was observed under visual inspection; the 6pt text was clear. Evaluation 3: Slight ink bleeding was observed under visual inspection, but it did not affect the design. Evaluation 2: Ink bleeding was observed under visual inspection, but 6pt text was still legible. Evaluation 1: Under visual inspection, the ink clearly bleeds and the 6pt text is illegible.

[0218] (Surface dryness) For the non-aqueous ink compositions of the Examples and Comparative Examples, surface drying properties were evaluated. Specifically, similar to the above evaluation of bleed properties, solid images were printed on a recording medium (polyvinyl chloride tape (IMAGin JT5829R: manufactured by MACtac)) in a high-quality printing mode (1440×720dpi), and the time elapsed until drying at 40°C was measured (denoted as "surface drying properties" in the table). Evaluation Criteria Rating 5: Dried in less than 2 minutes. Evaluation 4: Drying in a time of more than 2 minutes but less than 4 minutes. Evaluation 3: Drying time is between 4 minutes and 6 minutes. Evaluation 2: Drying time is between 6 minutes and 8 minutes. Evaluation 1: Drys within 8 minutes or more.

[0219] (Maintain stability) The storage stability of the non-aqueous ink compositions used in 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 volumetric cumulative 50% particle size (D50) of the pigment before and after the test were observed. Storage stability was evaluated according to the following criteria. Furthermore, the viscosity of the ink was measured using a falling ball viscometer (AMVn manufactured by Anton Paar) at 20°C, and the volumetric cumulative 50% particle size (D50) of the pigment was measured using a particle size distribution measuring device (NANOTRACWAVE particle size analyzer manufactured by MicrotracBEL Co., Ltd.) at 25°C. Furthermore, the following evaluation uses the larger of the change rates of "viscosity" and "volumetric cumulative 50% particle size (D50) of the pigment" as the evaluation of the non-aqueous ink composition (denoted as "storage stability" in the table). Evaluation Criteria Evaluation 5: The cumulative 50% particle size (D50) change rate of both viscosity and pigment volume was less than 3%. Evaluation 4: The rate of change of viscosity and pigment volume based on 50% particle size (D50) is greater than 3% but less than 5%. Evaluation 3: The rate of change of either viscosity or pigment volume based on 50% of particle size (D50) is greater than 5% but less than 8%. Evaluation 2: The rate of change of viscosity and pigment volume based on 50% particle size (D50) is greater than 8% but less than 10%. Evaluation 1: The rate of change of viscosity and pigment volume based on 50% particle size (D50) is more than 10%.

[0220] (concealment) The concealment properties of the non-aqueous ink compositions used in the Examples, Comparative Examples, and Reference Examples were evaluated. Specifically, similar to the blurring evaluation described above, solid areas were printed on a recording medium (transparent PVC adhesive tape (SCP-AS: manufactured by 3M)) in a high-quality printing mode (1440 × 720 dpi) at a substrate surface temperature of 40°C, and dried at room temperature for 1 day. Subsequently, the visible light transmittance was measured at 1 nm intervals within the range of 380 nm to 780 nm using a spectrophotometer (UV-1800: Shimadzu Corporation). The average value obtained by dividing the cumulative value by the number of measurements was recorded as the visible light transmittance. Evaluation Criteria Rating 5: Visible light transmittance is less than 10%. Evaluation 4: Visible light transmittance is less than 20% but more than 10%. Evaluation 3: Visible light transmittance is less than 30% but more than 20%. Evaluation 2: Visible light transmittance is less than 40% but more than 30%. Evaluation 1: Visible light transmittance is over 40%.

[0221] (Ejection stability) For the non-aqueous ink compositions of the Examples, Comparative Examples, and Reference Examples, the ejection stability was evaluated. Specifically, similar to the above-described bleeding evaluation, solid images and fine lines were continuously printed on a recording medium (polyvinyl chloride tape (IMAGin JT5829R: manufactured by MACtac)) in a high-quality printing mode (1440×720dpi) at a substrate surface temperature of 40°C. The presence of any omissions, ink splattering, or ink flight was visually observed, and the number of occurrences was counted (referred to as "ejection stability" in the table). Evaluation Criteria Rating 5: It can accurately reproduce fine lines. Evaluation 4: It can reproduce fine lines with basic accuracy. Evaluation 3: The fine line shows a slight bend. Evaluation 2: The ink droplet landing position is off, and bending is visible. Evaluation 1: The ink droplet landing position is severely off, making it impossible to reproduce fine lines.

[0222] (Cleanliness and Restoration) The evaluation assessed whether the cleaning action of the printer could clear the nozzle clogging when it occurred. Specifically, using an inkjet printer equipped with a cleaning system (trade name VersaArt RE-640, manufactured by Roland DG Inc.), the ink compositions of the examples and comparative examples were filled, and a solid image of 1.80 m2 was printed in a high-quality printing mode (1440×720 dpi). After being placed at room temperature (25°C) for one week, a nozzle check pattern was printed, and cleaning was performed until the nozzle check pattern no longer had any missing colors (referred to as "cleaning recoverability" in the table). Evaluation Criteria Rating 5: No missing colors. Rating 4: One cleaning cycle can remove nozzle blockage. Rating 3: Cleaning 2-3 times can remove nozzle blockage. Rating 2: Cleaning 4-5 times can remove nozzle blockage. Evaluation 1: The nozzle blockage was not cleared even after 6 cleanings.

[0223] [Table 2] Comparative Example 1-1 Comparative Examples 1-2 Comparative Examples 1-3 Example 1-1 Examples 1-2 Examples 1-3 Examples 1-4 Examples 1-5 Examples 1-6 Examples 1-7 Examples 1-8 Examples 1-9 Examples 1-10 Examples 1-11 Examples 1-12 Examples 1-13 Classification type name Flash point (°C) Organic solvent A Alkylamine solvents N,N-Dimethylformamide 58.0 Alkylamine solvents N,N-Diethylmethylamine 60.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 0.5 1.0 15.0 35.0 55.0 80.0 Alkylamine solvents N,N-Diethylpropionylamine 73.0 Alkylamine solvents N,N-Diethylacetamide 78.0 Cyclic amide solvents N-Methyl-ε-caprolactam 103.3 Cyclic amide solvents ε-caprolactam 125.0 Cyclic amide solvents N-Vinylcaprolactam 113.0 Cyclic amide solvents N-Methyl-2-pyrrolidone 86.1 Other organic solvents cyclic esters γ-Butyrolactone 101.0 cyclic esters ε-caprolactone 115.0 Dialkyl ethers Diethylene glycol diethyl ether 71.0 47.5 52.5 47.5 47.5 47.5 52.5 62.5 62.5 62.5 62.0 61.5 47.5 27.5 17.5 Dialkyl ethers Diethylene glycol methyl ethyl ether 64.0 10.0 52.5 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 Dialkyl ethers Dipropylene glycol dimethyl ether 65.0 Dialkyl ethers Diethylene glycol dibutyl ether 117.2 Monoalkyl ethers Triethylene glycol mono-n-butyl ether 156.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Monoalkyl ethers Diethylene glycol monobutyl ether 100.0 5.0 Monoalkyl ethers Dipropylene glycol monomethyl ether 76.5 5.0 5.0 5.0 Monoalkyl ethers Tetraethylene glycol monobutyl ether 166.0 5.0 Acetate 3-Methoxybutyl Acetate 62.5 carbonate Propylene carbonate 135.0 lactates Ethyl lactate 52.0 Diester Diethyl oxalate 76.0 Cyclic amides 3-Methyl-2-azolidinone 115.0 alcohol 3-Methoxybutanol 62.5 Alkoxypropylamine N,N-Dimethyl-β-methoxypropionic acid 67.9 resin acrylic resins Synthetic resin ① acrylic resins Synthetic resin ② acrylic resins Synthetic resin ③ 5.5 5.5 4.5 4.5 4.5 5.5 4.5 5.5 5.5 5.5 4.5 5.5 5.5 4.5 5.5 5.0 acrylic resins Synthetic resin ④ acrylic resins Synthetic resin ⑤ Vinyl chloride-vinyl acetate copolymer resin Synthetic resin ① 1.0 1.0 1.0 Vinyl chloride-vinyl acetate copolymer resin Synthetic resin ② Cellulose resin CAB-381-0.5 (Manufactured by Eastman Corporation) 1.0 1.0 1.0 Polyester resin Synthetic resins polyurethane resin Synthetic resins dispersant Solsperse20000 (Manufactured by Lubrizol) Solsperse33000 (Manufactured by Lubrizol) 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 3.5 surfactants Silicon-based additives BYK-331 (Manufactured by BYK) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Silicon-based additives BYK-313 (Manufactured by BYK) 0.5 0.5 0.5 Classification type Pigment particle size (nm) White pigment Titanium oxide (TiO2)1 203 12.0 12.0 12.0 12.0 12.0 12.0 12.0 12.0 12.0 12.0 12.0 12.0 12.0 12.0 12.0 11.0 Titanium oxide (TiO 2) 2 150 Titanium oxide (TiO 2) 3 315 Titanium oxide (TiO 2) 4 390 Titanium oxide (TiO2)5 430 total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 The ratio of resin content to white pigment content 0.46 0.46 0.46 0.46 0.46 0.46 0.46 0.46 0.46 0.46 0.46 0.46 0.46 0.46 0.46 0.45 evaluate Spreadability evaluation 5 5 5 5 5 5 5 2 2 2 3 3 5 5 5 5 Surface drying properties 5 5 5 5 5 4 5 1 1 1 2 3 5 5 5 5 Preservation stability 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Concealment 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 4 Ejection stability 5 5 5 5 4 5 5 3 3 3 5 5 5 5 5 5 Cleaning and Restoration 5 5 5 4 5 4 4 3 3 3 4 4 4 4 4 4

[0224] [Table 3] Comparative Examples 1-4 Comparative Examples 1-5 Examples 1-14 Examples 1-15 Examples 1-16 Examples 1-17 Examples 1-18 Examples 1-19 Examples 1-20 Examples 1-21 Examples 1-22 Examples 1-23 Examples 1-24 Examples 1-25 Examples 1-26 Examples 1-27 Classification type name Flash point (°C) Organic solvent A Alkylamine solvents N,N-Dimethylformamide 58.0 15.0 Alkylamine solvents N,N-Diethylmethylamine 60.0 85.0 93.0 15.0 15.0 15.0 15.0 15.0 Alkylamine solvents N,N-Diethylpropionylamine 73.0 15.0 Alkylamine solvents N,N-Diethylacetamide 78.0 15.0 Cyclic amide solvents N-Methyl-ε-caprolactam 103.3 15.0 Cyclic amide solvents ε-caprolactam 125.0 15.0 Cyclic amide solvents N-Vinylcaprolactam 113.0 15.0 Cyclic amide solvents N-Methyl-2-pyrrolidone 86.1 15.0 Other organic solvents cyclic esters γ-Butyrolactone 101.0 15.0 cyclic esters ε-caprolactone 115.0 15.0 Dialkyl ethers Diethylene glycol diethyl ether 71.0 47.5 47.5 47.5 47.5 47.5 47.5 47.5 47.5 47.5 47.5 47.5 47.5 47.5 47.5 Dialkyl ethers Diethylene glycol methyl ethyl ether 64.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 Dialkyl ethers Dipropylene glycol dimethyl ether 65.0 Dialkyl ethers Diethylene glycol dibutyl ether 117.2 Monoalkyl ethers Triethylene glycol mono-n-butyl ether 156.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Monoalkyl ethers Diethylene glycol monobutyl ether 100.0 Monoalkyl ethers Dipropylene glycol monomethyl ether 76.5 Monoalkyl ethers Tetraethylene glycol monobutyl ether 166.0 Acetate 3-Methoxybutyl Acetate 62.5 carbonates Propylene carbonate 135.0 lactates Ethyl lactate 52.0 Diester Diethyl oxalate 76.0 Cyclic amides 3-Methyl-2-azolidinone 115.0 alcohol 3-Methoxybutanol 62.5 Alkoxypropylamine N,N-Dimethyl-β-methoxypropionic acid 67.9 resin acrylic resins Synthetic resin ① acrylic resins Synthetic resin ② acrylic resins Synthetic resin ③ 4.0 3.0 5.5 5.5 5.5 5.5 5.5 4.5 4.5 4.5 5.5 5.5 5.5 4.5 5.5 acrylic resins Synthetic resin ④ acrylic resins Synthetic resin ⑤ Vinyl chloride-vinyl acetate copolymer resin Synthetic resin ① Vinyl chloride-vinyl acetate copolymer resin Synthetic resin ② Cellulose resin CAB-381-0.5 (Manufactured by Eastman Corporation) 5.5 Polyester resin Synthetic resins 1.0 1.0 1.0 polyurethane resin Synthetic resins 1.0 dispersant Solsperse20000 (Manufactured by Lubrizol) 4.5 4.5 4.5 4.5 4.5 Solsperse33000 (Manufactured by Lubrizol) 2.5 0.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 surfactants Silicon-based additives BYK-331 (Manufactured by BYK) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Silicon-based additives BYK-313 (Manufactured by BYK) Classification type Pigment particle size (nm) White pigment Titanium oxide (TiO2)1 203 8.0 3.0 12.0 12.0 12.0 12.0 12.0 12.0 12.0 12.0 12.0 12.0 Titanium oxide (TiO 2) 2 150 12.0 Titanium oxide (TiO 2) 3 315 12.0 Titanium oxide (TiO 2) 4 390 12.0 Titanium oxide (TiO2)5 430 12.0 total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 The ratio of resin content to white pigment content 0.50 1.00 0.46 0.46 0.46 0.46 0.46 0.46 0.46 0.46 0.46 0.46 0.46 0.46 0.46 0.46 evaluate Spreadability evaluation 5 5 5 5 5 2 2 4 4 4 4 5 5 5 5 5 Surface drying properties 5 5 5 5 5 4 4 5 5 5 5 5 5 5 5 5 Preservation stability 5 5 5 5 3 4 4 5 5 5 3 5 5 5 5 5 Concealment 3 1 5 5 5 5 5 5 5 5 5 4 5 5 5 5 Ejection stability 5 5 5 5 4 5 5 5 5 5 5 5 5 5 2 5 Cleaning and Restoration 4 4 4 4 4 4 4 4 4 4 4 4 4 4 3 4

[0225] [Table 4] Examples 1-28 Examples 1-29 Examples 1-30 Examples 1-31 Examples 1-32 Examples 1-33 Examples 1-34 Examples 1-35 Examples 1-36 Examples 1-37 Examples 1-38 Examples 1-39 Examples 1-40 Examples 1-41 Examples 1-42 Examples 1-43 Classification type name Flash point (°C) Organic solvent A Alkylamine solvents N,N-Dimethylformamide 58.0 Alkylamine solvents N,N-Diethylmethylamine 60.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 Alkylamine solvents N,N-Diethylpropionylamine 73.0 Alkylamine solvents N,N-Diethylacetamide 78.0 Cyclic amide solvents N-Methyl-ε-caprolactam 103.3 Cyclic amide solvents ε-caprolactam 125.0 Cyclic amide solvents N-Vinylcaprolactam 113.0 Cyclic amide solvents N-Methyl-2-pyrrolidone 86.1 Other organic solvents cyclic esters γ-Butyrolactone 101.0 10.0 cyclic esters ε-caprolactone 115.0 10.0 Dialkyl ethers Diethylene glycol diethyl ether 71.0 47.5 47.5 49.0 49.0 51.0 50.0 45.0 49.0 48.0 48.0 37.5 37.5 37.5 37.5 37.5 37.5 Dialkyl ethers Diethylene glycol methyl ethyl ether 64.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 Dialkyl ethers Dipropylene glycol dimethyl ether 65.0 Dialkyl ethers Diethylene glycol dibutyl ether 117.2 Monoalkyl ethers Triethylene glycol mono-n-butyl ether 156.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Monoalkyl ethers Diethylene glycol monobutyl ether 100.0 Monoalkyl ethers Dipropylene glycol monomethyl ether 76.5 Monoalkyl ethers Tetraethylene glycol monobutyl ether 166.0 Acetate 3-Methoxybutyl Acetate 62.5 10.0 carbonates Propylene carbonate 135.0 10.0 lactates Ethyl lactate 52.0 10.0 Diester Diethyl oxalate 76.0 10.0 Cyclic amides 3-Methyl-2-azolidinone 115.0 alcohol 3-Methoxybutanol 62.5 Alkoxypropylamine N,N-Dimethyl-β-methoxypropionic acid 67.9 resin acrylic resins Synthetic resin ① 3.0 acrylic resins Synthetic resin ② 3.5 acrylic resins Synthetic resin ③ 2.0 3.0 8.0 8.0 9.0 5.5 5.5 5.5 5.5 5.5 5.5 5.5 acrylic resins Synthetic resin ④ 2.0 acrylic resins Synthetic resin ⑤ 2.0 Vinyl chloride-vinyl acetate copolymer resin Synthetic resin ① 2.5 Vinyl chloride-vinyl acetate copolymer resin Synthetic resin ② 2.0 Cellulose resin CAB-381-0.5 (Manufactured by Eastman Corporation) Polyester resin Synthetic resins 2.0 polyurethane resin Synthetic resins 2.0 dispersant Solsperse20000 (Manufactured by Lubrizol) 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 Solsperse33000 (Manufactured by Lubrizol) 4.5 4.5 4.5 4.5 4.5 4.5 surfactants Silicon-based additives BYK-331 (Manufactured by BYK) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Silicon-based additives BYK-313 (Manufactured by BYK) Classification type Pigment particle size (nm) White pigment Titanium oxide (TiO2)1 203 12.0 12.0 12.0 12.0 12.0 12.0 12.0 8.0 8.0 12.0 12.0 12.0 12.0 12.0 12.0 12.0 Titanium oxide (TiO 2) 2 150 Titanium oxide (TiO 2) 3 315 Titanium oxide (TiO 2) 4 390 Titanium oxide (TiO2)5 430 total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 The ratio of resin content to white pigment content 0.46 0.46 0.33 0.33 0.17 0.25 0.67 1.00 1.13 0.46 0.46 0.46 0.46 0.46 0.46 0.46 evaluate Spreadability evaluation 5 5 5 5 5 5 5 5 5 4 5 5 5 5 5 5 Surface drying properties 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Preservation stability 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Concealment 5 5 5 5 2 5 5 5 4 5 5 5 5 5 5 5 Ejection stability 5 5 5 5 5 5 5 3 2 5 5 5 5 5 5 5 Cleaning and Restoration 4 4 4 4 4 4 4 5 5 4 4 4 4 4 4 4

[0226] [Table 5] Examples 1-44 Examples 1-45 Examples 1-46 Examples 1-47 Examples 1-48 Examples 1-49 Examples 1-50 Examples 1-51 Examples 1-52 Examples 1-53 Examples 1-54 Examples 1-55 Examples 1-56 Examples 1-57 Examples 1-58 Classification type name Flash point (°C) Organic solvent A Alkylamine solvents N,N-Dimethylformamide 58.0 Alkylamine solvents N,N-Diethylmethylamine 60.0 15.0 15.0 15.0 67.5 67.5 67.5 67.5 67.5 67.5 67.5 67.5 67.5 15.0 15.0 15.0 Alkylamine solvents N,N-Diethylpropionylamine 73.0 Alkylamine solvents N,N-Diethylacetamide 78.0 Cyclic amide solvents N-Methyl-ε-caprolactam 103.3 Cyclic amide solvents ε-caprolactam 125.0 Cyclic amide solvents N-Vinylcaprolactam 113.0 Cyclic amide solvents N-Methyl-2-pyrrolidone 86.1 Other organic solvents cyclic esters γ-Butyrolactone 101.0 10.0 cyclic esters ε-caprolactone 115.0 10.0 Dialkyl ethers Diethylene glycol diethyl ether 71.0 37.5 37.5 37.5 44.5 39.5 34.5 Dialkyl ethers Diethylene glycol methyl ethyl ether 64.0 10.0 10.0 10.0 10.0 10.0 10.0 Dialkyl ethers Dipropylene glycol dimethyl ether 65.0 Dialkyl ethers Diethylene glycol dibutyl ether 117.2 Monoalkyl ethers Triethylene glycol mono-n-butyl ether 156.0 5.0 5.0 5.0 5.0 5.0 5.0 Monoalkyl ethers Diethylene glycol monobutyl ether 100.0 Monoalkyl ethers Dipropylene glycol monomethyl ether 76.5 Monoalkyl ethers Tetraethylene glycol monobutyl ether 166.0 Acetate 3-Methoxybutyl Acetate 62.5 10.0 carbonates Propylene carbonate 135.0 10.0 lactates Ethyl lactate 52.0 10.0 Diester Diethyl oxalate 76.0 10.0 Cyclophenylamine 3-Methyl-2-azolidinone 115.0 10.0 10.0 alcohol 3-Methoxybutanol 62.5 10.0 10.0 Alkoxypropylamine N,N-Dimethyl-β-methoxypropionic acid 67.9 10.0 10.0 Resin acrylic resins Synthetic resin① acrylic resins Synthetic resin ② acrylic resins Synthetic resin ③ 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 acrylic resins Synthetic resin ④ acrylic resins Synthetic resin ⑤ Vinyl chloride-vinyl acetate copolymer resin Synthetic resin ① Vinyl chloride-vinyl acetate copolymer resin Synthetic resin ② Cellulose resin CAB-381-0.5 (Manufactured by Eastman Corporation) Polyester resin Synthetic resins polyurethane resin Synthetic resins dispersant Solsperse20000 (Manufactured by Lubrizol) Solsperse33000 (Manufactured by Lubrizol) 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 surfactants Silicon-based additives BYK-331 (Manufactured by BYK) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Silicon-based additives BYK-313 (Manufactured by BYK) Classification type Pigment particle size (nm) White pigment Titanium oxide (TiO2)1 203 12.0 12.0 12.0 12.0 12.0 12.0 12.0 12.0 12.0 12.0 12.0 12.0 15.0 20.0 23.0 Titanium oxide (TiO 2) 2 150 Titanium oxide (TiO 2) 3 315 Titanium oxide (TiO 2) 4 390 Titanium oxide (TiO2)5 430 total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 98.0 The ratio of resin content to white pigment content 0.46 0.46 0.46 0.46 0.46 0.46 0.46 0.46 0.46 0.46 0.46 0.46 0.37 0.28 0.24 evaluate Spreadability evaluation 5 5 5 5 5 4 5 5 4 4 5 5 5 5 5 Surface drying properties 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Preservation stability 5 5 5 3 3 3 3 3 3 3 3 3 5 4 3 Concealment 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Ejection stability 5 5 5 5 5 5 5 5 5 5 5 5 5 4 3 Cleaning and Restoration 4 4 4 5 5 4 4 4 4 4 4 4 4 4 2

[0227] As shown in the table above, it can be seen that if the non-aqueous ink composition of the embodiment containing organic solvent A (selected from at least one of the group consisting of alkyl amide solvents (a1) and cyclic amide solvents (a2)) is a non-aqueous ink composition containing white pigment, it can also have both high cleanability and surface drying properties on the substrate.

[0228] In particular, in the non-aqueous ink compositions of Examples 1-8 to 1-13 in which the content of organic solvent A (alkylamide solvent) was changed, especially in Examples 1-9 to 1-13 in which the content of organic solvent A (alkylamide solvent) (a1) was in the range of 1% to 90% by mass, compared with Examples 1-8, records with higher cleanability and better surface drying properties were also obtained.

[0229] Furthermore, in the non-aqueous ink compositions of Examples 1-1, 1-23 to 1-26, which changed the volumetric cumulative 50% particle size (D50) of the white pigment contained therein, especially in the non-aqueous ink compositions of Examples 1-1, 1-23 to 1-25, where the volumetric cumulative 50% particle size (D50) of the white pigment was in the range of 50 nm to 400 nm, compared with Examples 1-26, records with higher cleanability and better surface drying properties were also obtained.

[0230] Furthermore, the non-aqueous ink compositions of Examples 1-1, 1-16 to 1-22, in which the type of organic solvent A is varied between alkyl amide solvents (a1) and cyclic amide solvents (a2), all exhibit the effects of the present invention.

[0231] Furthermore, the non-aqueous ink compositions of Examples 1-1, 1-29 to 1-31, which vary the type of resin contained, all exhibit the effects of the present invention.

[0232] Furthermore, the non-aqueous ink compositions of Examples 1-1, 1-30~1-31, and 1-33~1-35, in which the resin content to white pigment content ratio is 0.20~1.00, exhibit better concealment than Example 1-32 and better ejection stability than Example 36.

[0233] Furthermore, the non-aqueous ink compositions of Examples 1-38 to 1-46, which use different types of organic solvents, all exhibit the effects of the present invention.

[0234] On the other hand, the non-aqueous ink compositions of Comparative Examples 1-1 to 1-5, which do not contain organic solvent A (selected from at least one of the group consisting of alkyl amide solvents (a1) and cyclic amide solvents (a2), have reduced surface drying properties and do not exert the effects of the present invention.

[0235] (Second Implementation) 1. Resin Production (1) Acrylic resins A mixture of 150 g of methyl methacrylate, 50 g of butyl methacrylate, and a specific amount of tributyl peroxide (2-ethylhexanoate) (polymerization initiator) was added dropwise over 1.5 hours to 300 g of diethylene glycol diethyl ether at 100°C. After the addition was complete, the mixture was reacted at 100°C for 2 hours and then cooled to obtain a colorless and transparent polymer solution of methyl methacrylate. Subsequently, the solvent was thoroughly removed from the polymer solution by distillation to obtain the polymer of methyl methacrylate. By varying the amount of tributyl peroxide (2-ethylhexanoate) used as the polymerization initiator, the average molecular weight of the polymerized methyl methacrylate (acrylic resin) was controlled to be 10,000~105,000 (the mass of the polymerization initiator used at this time is recorded in Table 6 below. Table 6 is labeled "starting dose").

[0236] (2) Vinyl chloride-vinyl acetate copolymer resin In a high-pressure reactor equipped with a stirring device, after nitrogen purging, 100 parts by weight of deionized water, 40 parts by weight of methanol, 32 parts by weight of vinyl chloride, 5 parts by weight of vinyl acetate, 0.2 parts by weight of glycidyl methacrylate, 3.55 parts by weight of hydroxypropyl acrylate, 0.1 parts by weight of hydroxypropyl methylcellulose (suspending agent), 0.026 parts by weight of di(2-ethylhexyl) peroxide dicarbonate (polymerization initiator), and a specific amount of di-3,5,5-trimethylhexanol peroxide (polymerization initiator) were added. Under a nitrogen atmosphere, the mixture was stirred and heated to 63°C. Immediately after reaching 63°C, 48 parts by weight of vinyl chloride were continuously injected over a period of 6 hours, followed by a 5.4-hour injection of a mixture of 0.6 parts by weight of glycidyl methacrylate and 10.65 parts by weight of hydroxypropyl acrylate to initiate a copolymerization reaction. When the pressure inside the high-pressure reactor reached 0.3 MPa, the residual pressure was released, and the resin slurry was cooled, filtered, and dried to obtain a vinyl chloride-based copolymer resin. By changing the amount of di-3,5,5-trimethylhexanol peroxide used as the polymerization initiator, the average molecular weight of the vinyl chloride-vinyl acetate copolymer resin was controlled to be 40,000 to 90,000 (the mass of the polymerization initiator used at this time is recorded in Table 6 below. Table 6 is denoted as "Initiating Dosage").

[0237] [Table 6] Weight average molecular weight (Relative molecular mass) Starting dose (g) acrylic resin Synthetic resin ① Mw=15000 3.30 Synthetic resin ② Mw=30000 1.20 Vinyl chloride-vinyl acetate copolymer resin Synthetic resin ① Mw=40000 0.58

[0238] (3) 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 added to a round-bottom flask. The mixture was slowly heated to 240°C over 4 hours, while the distillate was discharged from the system and the esterification reaction was carried out. After the esterification reaction was completed, the pressure was reduced to 10 mmHg over 30 minutes, and the temperature was raised to 250°C for initial polymerization. Subsequently, secondary polymerization was carried out at a pressure below 1 mmHg for 1 hour to obtain a polyester resin.

[0239] (4) Polyurethane resin 192.5 parts by weight of polycarbonate diol (PLACCEL CD-220: manufactured by Daicel), 41.6 parts by weight of isophorone diisocyanate (IPDI: manufactured by Evonik), and 100 parts by weight of N,N-diethylmethylamine (DEF) were added to a round-bottom flask and mixed evenly. Then, a mixture of 0.01 parts by weight of T100BHJ (catalyst) and 0.09 parts by weight of N,N-diethylmethylamine (DEF) was added and reacted at 75°C for 3 hours to obtain a prepolymer with isocyanate groups at the ends. 250 parts by weight of N,N-diethylmethylformamide (DEF) were added and dissolved uniformly. Then, a chain elongating agent solution prepared by dissolving 12 parts by weight of 3-aminomethyl-3,5,5-trimethylcyclohexylamine (IPD: manufactured by Evonik) in 100 parts by weight of N,N-diethylmethylformamide (DEF) was added, and the mixture was stirred at 60°C for 40 minutes. Subsequently, a reaction terminator prepared by dissolving 3.8 parts by weight of monoisopropanolamine (MIPA: manufactured by Daicel) in 50 parts by weight of N,N-diethylmethylformamide was added. Finally, 250 parts by weight of N,N-diethylmethylformamide (DEF) was added to obtain a polyurethane solution with a solid content of 25.0%.

[0240] 2. Production of glossy pigments (1) Glossy pigments 1 The following composition of coating liquid 1 is uniformly coated on a 100 μm thick PET film using a rod coating method, and dried at 60°C for 10 minutes to form a release resin layer.

[0241] Coating liquid 1 • Cellulose acetate butyrate (butylation rate 35-39%, manufactured by Kanto Chemical Co., Ltd.) 3% Isopropanol 97%

[0242] Secondly, using a "VE-1010 vacuum evaporation apparatus" manufactured by VACUUM DEVICE Co., Ltd., a 20 nm thick metal-containing thin film was formed on the release resin layer to create a laminate. The obtained laminate was immersed in an organic solvent and simultaneously subjected to release, pulverization, and micro-dispersion treatment for 12 hours using a "VS-150 ultrasonic disperser" manufactured by AS ONE Co., Ltd., to obtain a bright pigment dispersion containing the organic solvent and a bright pigment (including a metal-containing bright pigment containing aluminum). Furthermore, the "organic solvent" used was the solvent with the highest content among the solvents contained in the non-aqueous ink compositions of the examples and comparative examples described later.

[0243] The obtained glossy pigment dispersion was filtered using a 5 μm SUS sieve filter to remove coarse particles. Subsequently, the concentration of the glossy pigment was adjusted to prepare a glossy pigment dispersion 1 containing 5% by mass of glossy pigment 1. The glossy pigment 1 had a volumetric 50% particle size (D50) of 1.5 μm, a volumetric 90% particle size (D90) of 3.5 μm, and a thickness of 20 nm.

[0244] (2) Glossy Pigment 2 A glossy pigment dispersion was prepared using the same method as described above. 200 g of the glossy pigment dispersion was mixed with the solution obtained by dissolving 5 g of stearic acid in 100 g of acetone. After stirring for 1 hour, the above-described centrifugation and washing processes were performed to replace the acetone with an organic solvent (the solvent with the highest content among the solvents contained in the non-aqueous ink compositions of the examples and comparative examples described later). A glossy pigment dispersion 2 containing 5% by mass of glossy pigment 2 was prepared. The glossy pigment 2 has a volumetric cumulative 50% particle size (D50) of 1.5 μm, a volumetric cumulative 90% particle size (D90) of 3.2 μm, and a thickness of 20 nm.

[0245] (3) Glossy pigments 3 In the manufacture of the aforementioned glossy pigment 1, the film thickness of the metal-containing film, the micronization process, and the mesh size of the screen filter were changed to prepare a glossy pigment dispersion 3 containing 5% by mass of glossy pigment 3. The glossy pigment 3 has a volume-based cumulative 50% particle size (D50) of 4.8 μm, a volume-based cumulative 90% particle size (D90) of 8.2 μm, and a thickness of 100 nm.

[0246] (4) Glossy pigments 4 In the manufacture of the aforementioned glossy pigment 1, the film thickness of the metal-containing film, the micronization process, and the mesh size of the sieve filter were changed to prepare a glossy pigment dispersion 4 containing glossy pigment 4. The glossy pigment 4 has a volume-based cumulative 50% particle size (D50) of 3.0 μm, a volume-based cumulative 90% particle size (D90) of 5.0 μm, and a thickness of 1000 nm.

[0247] (5) Glossy pigments 5 In the manufacture of the aforementioned glossy pigment 1, aluminum is replaced with indium, and the film thickness, micronization treatment, and mesh size of the metal-containing film and screen filter are changed to prepare a glossy pigment dispersion 5 containing glossy pigment 5. The glossy pigment 5 has a volume-based cumulative 50% particle size (D50) of 0.05 μm, a volume-based cumulative 90% particle size (D90) of 1.0 μm, and a thickness of 5 nm.

[0248] (6) Glossy pigments 6 In the manufacture of the aforementioned glossy pigment 1, aluminum was replaced with nickel, and the film thickness, micronization treatment, and mesh size of the metal-containing film and screen filter were changed to prepare a glossy pigment dispersion 6 containing glossy pigment 6. The glossy pigment 5 has a volume-based cumulative 50% particle size (D50) of 3.8 μm, a volume-based cumulative 90% particle size (D90) of 5.0 μm, and a thickness of 5 nm.

[0249] 3. Manufacturing of non-water-based ink compositions The non-aqueous ink compositions of the Examples and Comparative Examples were prepared according to the ratios shown in the table below, using various organic solvents, resins, dispersants, and glossy pigments. Specifically, the non-aqueous ink compositions of the Examples and Comparative Examples were adjusted using glossy pigment dispersions, organic solvents, resins, dispersants, and additives according to the ratios shown in the table below. Units are by mass%.

[0250] 4. Evaluation (Spreading properties) For the non-aqueous ink compositions of the Examples and Comparative Examples, the blurring properties were evaluated. Specifically, using an inkjet printer (trade name VersaArt RE-640, manufactured by Roland DG Inc.), the non-aqueous ink compositions of the Examples and Comparative Examples were printed by inkjet printing on a recording medium (PVC adhesive tape (IMAGin JT5829R: manufactured by MACtac)) in high-quality printing mode (1440×720dpi) at a substrate surface temperature of 40°C. Images of 6pt text with different colors in solid areas compared to solid areas were printed. The printed text was dried in an oven at 60°C for 5 minutes, and the blurring properties of the printed text were observed under a visual magnifying glass (×10) (referred to as "blurring properties" in the table). Evaluation Criteria Evaluation 5: No ink spreading was observed under a magnifying glass. Evaluation 4: No ink bleeding was observed under visual inspection; the 6pt text was clear. Evaluation 3: Slight ink bleeding was observed under visual inspection, but it did not affect the design. Evaluation 2: Ink bleeding was observed under visual inspection, but 6pt text was still legible. Evaluation 1: Under visual inspection, the ink clearly bleeds and the 6pt text is illegible.

[0251] (Surface dryness) For the non-aqueous ink compositions of the Examples and Comparative Examples, surface drying properties were evaluated. Specifically, similar to the above-described bleeding property evaluation, solid images were printed on a recording medium (polyvinyl chloride tape (IMAGin JT5829R: manufactured by MACtac)) in a high-quality printing mode (1440×720dpi), and the time elapsed until drying at 40°C was measured (referred to as "surface drying property" in the table). Evaluation Criteria Rating 5: Dried in less than 2 minutes. Evaluation 4: Drying in a time of more than 2 minutes but less than 4 minutes. Evaluation 3: Drying time is between 4 minutes and 6 minutes. Evaluation 2: Drying time is between 6 minutes and 8 minutes. Evaluation 1: Drys within 8 minutes or more.

[0252] (Maintain stability) The storage stability of the non-aqueous ink compositions in the examples and comparative examples was evaluated. Specifically, the non-aqueous ink compositions were stored at 60°C for one month, and the changes in viscosity and the volumetric 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. Furthermore, the viscosity of the ink was measured using a falling ball viscometer (AMVn manufactured by Anton Paar) at 20°C, and the volumetric cumulative 50% particle size (D50) of the pigment was measured using a particle size distribution measuring device (NANOTRACWAVE particle size analyzer manufactured by MicrotracBEL Co., Ltd.) at 25°C. Furthermore, the following evaluation uses the larger of the change rates of "viscosity" and "volumetric cumulative 50% particle size (D50) of the pigment" as the evaluation of the non-aqueous ink composition (denoted as "storage stability" in the table). Evaluation Criteria Evaluation 5: The cumulative 50% particle size (D50) change rate of both viscosity and pigment volume was less than 3%. Evaluation 4: The rate of change of viscosity and pigment volume based on 50% particle size (D50) is greater than 3% but less than 5%. Evaluation 3: The rate of change of either viscosity or pigment volume based on 50% of particle size (D50) is greater than 5% but less than 8%. Evaluation 2: The rate of change of viscosity and pigment volume based on 50% particle size (D50) is greater than 8% but less than 10%. Evaluation 1: The rate of change of viscosity and pigment volume based on 50% particle size (D50) is more than 10%.

[0253] (Ejection stability) For the non-aqueous ink compositions of the examples and comparative examples, the ejection stability was evaluated. Specifically, similar to the above-described bleeding evaluation, solid images and fine lines were continuously printed on a recording medium (polyvinyl chloride tape (IMAGin JT5829R: manufactured by MACtac)) in a high-quality printing mode (1440×720dpi) at a substrate surface temperature of 40°C. The presence of any missing dots, flying bends, or ink splatter was visually observed, and the number of occurrences was counted (referred to as "ejection stability" in the table). Evaluation Criteria Rating 5: It can accurately reproduce fine lines. Evaluation 4: It can reproduce fine lines with basic accuracy. Evaluation 3: The fine line shows a slight bend. Evaluation 2: The ink droplet landing position is off, and bending is visible. Evaluation 1: The ink droplet landing position is severely off, making it impossible to reproduce fine lines.

[0254] (Nozzle clogging evaluation) For the non-aqueous ink compositions of the Examples, Comparative Examples, and Reference Examples, nozzle clogging of the inks mounted in a printer was evaluated. Specifically, the ink compositions of the Examples and Comparative Examples were filled into an inkjet printer (trade name VersaArt RE-640, manufactured by Roland DG Co., Ltd.), and a nozzle check pattern was printed to confirm that all nozzles ejected ink. Subsequently, the printhead was moved back and forth for 30 minutes without ejecting ink, and the nozzle check pattern was printed again to count the number of nozzles that did not eject ink. The printer operating environment was set to room temperature of 40°C and relative humidity of 60% (referred to as "Nozzle Clogging Evaluation" in the table). Evaluation Criteria Rating 5: No inkjet printing for less than 5 prints. Rating 4: 6-10 inkjet printers not printing. Rating 3: 11-15 inkjet lines not printing. Rating 2: 16-20 inkjet lines not printing Rating 1: No inkjet printing for more than 21 lines.

[0255] (Glossiness) The gloss of printed materials obtained using the non-aqueous ink compositions of the Examples and Comparative Examples was evaluated. Specifically, similar to the above evaluation of ink spreadability, the ink was sprayed onto the surface of a recording medium (polyvinyl chloride tape (IMAGin JT5829R: manufactured by MACtac)) and dried to produce printed materials. For the obtained printed materials, a multi-angle colorimetric system CM-M6 manufactured by Konica Minolta was used. The incident light was directed from the printed surface to the gloss layer at an incident angle of 45°. The measurement angle was defined as the angle by which the reflection angle corresponding to the incident angle was changed by 15° towards the normal direction. The L* value in the L*a*b* colorimetric system at the measurement angle was measured, and the gloss was evaluated according to the following evaluation criteria (denoted as "gloss" in the table). Evaluation Criteria Rating 5: Brightness index is above 120. Rating 4: Brightness index is above 110 but below 120. Rating 3: Brightness index is above 100 but below 110. Rating 2: Brightness index is above 90 but below 100. Evaluation 1: Brightness index not reaching 90.

[0256] (Cleanliness and Restoration) For the non-aqueous ink compositions of the Examples and Comparative Examples, the ability of the printer's cleaning action to clear nozzle clogging when it occurs was evaluated. Specifically, using an inkjet printer equipped with a cleaning system (trade name VersaArt RE-640, manufactured by Roland DG Inc.), the ink compositions of the Examples and Comparative Examples were filled, and a solid image of 1.80 m2 was printed in high-quality printing mode (1440×720 dpi). After being placed at room temperature (25°C) for 1 day, a nozzle check pattern was printed, and cleaning was performed until the nozzle check pattern no longer had any missing colors (referred to as "cleaning recoverability" in the table). Evaluation Criteria Rating 5: Cleaning 0 to 4 times can clear nozzle blockage. Rating 4: Cleaning 5 to 6 times can clear nozzle blockage. Rating 3: Cleaning 7 to 8 times can clear nozzle blockage. Rating 2: Cleaning 9 to 10 times can clear nozzle blockage. Evaluation 1: Even after 10 cleaning attempts, the nozzle blockage could not be cleared.

[0257] [Table 7] Comparative Example 2-1 Comparative Example 2-2 Comparative Examples 2-3 Comparative Examples 2-4 Example 2-1 Example 2-2 Example 2-3 Examples 2-4 Examples 2-5 Examples 2-6 Examples 2-7 Examples 2-8 Examples 2-9 Example 2-10 Example 2-11 Example 2-12 Classification type name Flash point (°C) Organic solvent A Alkylamine solvents N,N-Dimethylformamide 58.0 Alkylamine solvents N,N-Diethylmethylamine 60.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 0.9 10.0 35.0 55.0 81.0 Alkylamine solvents N,N-Diethylpropionylamine 73.0 Alkylamine solvents N,N-Diethylacetamide 78.0 Cyclic amide solvents N-Methyl-ε-caprolactam 103.3 Cyclic amide solvents ε-caprolactam 125.0 Cyclic amide solvents N-Vinylcaprolactam 113.0 Cyclic amide solvents N-Methyl-2-pyrrolidone 86.1 Other organic solvents cyclic esters γ-Butyrolactone 101.0 10.0 cyclic esters ε-caprolactone 115.0 Dialkyl ethers Diethylene glycol methyl ethyl ether 64.0 20.0 20.0 20.0 20.0 20.0 30.0 30.0 89.9 31.0 31.0 34.9 14.9 8.9 Dialkyl ethers Diethylene glycol diethyl ether 71.0 60.0 59.9 74.9 60.0 59.9 50.0 65.0 59.9 59.9 89.9 58.0 48.9 20.0 20.0 5.0 Dialkyl ethers Dipropylene glycol dimethyl ether 65.0 20.0 Monoalkyl ethers Dipropylene glycol monomethyl ether 76.5 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Monoalkyl ethers Diethylene glycol monobutyl ether 100.0 5.0 5.0 Monoalkyl ethers Triethylene glycol mono-n-butyl ether 156.0 5.0 Monoalkyl ethers Tetraethylene glycol monobutyl ether 166.0 5.0 Acetate Triethylene glycol mono-n-butyl ether acetate 290.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Acetate Diethylene glycol mono-n-butyl ether acetate 107.0 carbonates Propylene carbonate 135.0 lactates Ethyl lactate 52.0 Diester Diethyl oxalate 76.0 Cyclic amides 3-Methyl-2-azolidinone 115.0 alcohol 3-Methoxybutanol 62.5 Alkoxypropylamine N,N-Dimethyl-β-methoxypropionic acid 67.9 resin acrylic resins Synthetic resin ① acrylic resins Synthetic resin ② 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Vinyl chloride-vinyl acetate copolymer resin Synthetic resin ① Cellulose resin CAB-381-0.5 (Manufactured by Eastman Corporation) Cellulose resin CAP-482-0.5 (Manufactured by Eastman Corporation) Polyester resin Synthetic resins polyurethane resin Synthetic resins dispersant Solsperse20000 (Manufactured by Lubrizol) Solsperse33000 (Manufactured by Lubrizol) additive Additive 1 (surfactants) UV3500 (Manufactured by BYK) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Additive 2 (surfactants) BYK-331 (Manufactured by BYK) pigment Glossy Pigment 1 Synthetic product 1 Glossy Pigment 2 Synthetic product 2 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Glossy Pigment 3 Synthetic product 3 Glossy Pigment 4 Synthetic product 4 Glossy Pigment 5 Synthetic product 5 Glossy Pigment 6 Synthetic product 6 total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 evaluate Spreading 5 5 5 5 5 5 5 5 5 5 5 3 5 5 5 5 Surface drying properties 5 5 5 5 5 5 5 1 1 1 1 3 5 5 5 5 Preservation stability 5 5 5 5 5 5 5 4 4 4 4 5 5 5 5 5 Ejection stability 5 5 5 5 5 5 5 3 3 3 3 5 5 5 5 5 Nozzle clogging evaluation 4 4 4 5 5 5 4 4 4 4 1 4 4 4 4 4 gloss 5 5 5 5 5 5 5 3 3 3 3 4 5 5 5 5 Cleaning and Restoration 5 5 5 5 5 5 5 1 1 1 1 5 5 5 5 5

[0258] [Table 8] Comparative Examples 2-5 Comparative Examples 2-6 Example 2-13 Example 2-14 Example 2-15 Example 2-16 Example 2-17 Example 2-18 Example 2-19 Example 2-20 Example 2-21 Example 2-22 Example 2-23 Example 2-24 Example 2-25 Example 2-26 Classification type name Flash point (°C) Organic solvent A Alkylamine solvents N,N-Dimethylformamide 58.0 10.0 Alkylamine solvents N,N-Diethylmethylamine 60.0 84.0 81.0 91.0 10.0 10.0 10.0 10.0 Alkylamine solvents N,N-Diethylpropionylamine 73.0 10.0 Alkylamine solvents N,N-Diethylacetamide 78.0 10.0 Cyclic amide solvents N-Methyl-ε-caprolactam 103.3 10.0 Cyclic amide solvents ε-caprolactam 125.0 10.0 Cyclic amide solvents N-Vinylcaprolactam 113.0 10.0 Cyclic amide solvents N-Methyl-2-pyrrolidone 86.1 10.0 Other organic solvents cyclic esters γ-Butyrolactone 101.0 10.0 cyclic esters ε-caprolactone 115.0 10.0 Dialkyl ethers Diethylene glycol methyl ethyl ether 64.0 8.9 13.9 4.9 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 Dialkyl ethers Diethylene glycol diethyl ether 71.0 5.0 1.0 59.9 59.9 59.9 59.9 59.9 59.9 59.9 59.9 59.9 60.5 56.5 60.5 60.5 Dialkyl ethers Dipropylene glycol dimethyl ether 65.0 Monoalkyl ethers Dipropylene glycol monomethyl ether 76.5 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Monoalkyl ethers Diethylene glycol monobutyl ether 100.0 Monoalkyl ethers Triethylene glycol mono-n-butyl ether 156.0 Monoalkyl ethers Tetraethylene glycol monobutyl ether 166.0 Acetate Triethylene glycol mono-n-butyl ether acetate 290.0 3.0 1.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Acetate Diethylene glycol mono-n-butyl ether acetate 107.0 carbonates Propylene carbonate 135.0 lactates Ethyl lactate 52.0 Diester Diethyl oxalate 76.0 Cyclic amides 3-Methyl-2-azolidinone 115.0 alcohol 3-Methoxybutanol 62.5 Alkoxypropylamine N,N-Dimethyl-β-methoxypropionic acid 67.9 resin acrylic resins Synthetic resin ① acrylic resins Synthetic resin ② 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Vinyl chloride-vinyl acetate copolymer resin Synthetic resin ① Cellulose resin CAB-381-0.5 (Manufactured by Eastman Corporation) Cellulose resin CAP-482-0.5 (Manufactured by Eastman Corporation) Polyester resin Synthetic resins Polyurethane resin Synthetic resins dispersant Solsperse20000 (Manufactured by Lubrizol) Solsperse33000 (Manufactured by Lubrizol) additive Additive 1 (surfactants) UV3500 (Manufactured by BYK) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Additive 2 (surfactants) BYK-331 (Manufactured by BYK) 0.1 0.1 0.1 pigment Glossy Pigment 1 Synthetic product 1 5.0 Glossy Pigment 2 Synthetic product 2 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Glossy Pigment 3 Synthetic product 3 1.0 Glossy Pigment 4 Synthetic product 4 Glossy Pigment 5 Synthetic product 5 1.0 Glossy Pigment 6 Synthetic product 6 1.0 total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 evaluate Spreading 5 5 5 5 5 5 4 4 4 4 4 4 5 5 5 5 Surface drying properties 5 5 5 5 5 5 5 5 5 5 4 3 5 5 5 5 Preservation stability 3 5 3 5 5 5 5 5 5 3 1 1 5 5 5 4 Ejection stability 5 5 4 5 5 5 5 5 5 5 5 5 5 5 5 5 Nozzle clogging evaluation 4 4 4 4 4 4 4 4 4 3 4 4 4 4 5 4 gloss 5 5 5 5 5 5 5 5 5 5 3 3 4 5 5 5 Cleaning and Restoration 5 5 4 5 5 5 5 5 5 5 2 2 5 5 5 4

[0259] [Table 9] Example 2-27 Example 2-28 Example 2-29 Examples 2-30 Example 2-31 Example 2-32 Example 2-33 Examples 2-34 Example 2-35 Examples 2-36 Example 2-37 Example 2-38 Example 2-39 Example 2-40 Example 2-41 Example 2-42 Classification type name Flash point (°C) Organic solvent A Alkylamine solvents N,N-Dimethylformamide 58.0 Alkylamine solvents N,N-Diethylmethylamine 60.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 Alkylamine solvents N,N-Diethylpropionylamine 73.0 Alkylamine solvents N,N-Diethylacetamide 78.0 Cyclic amide solvents N-Methyl-ε-caprolactam 103.3 Cyclic amide solvents ε-caprolactam 125.0 Cyclic amide solvents N-Vinylcaprolactam 113.0 Cyclic amide solvents N-Methyl-2-pyrrolidone 86.1 Other organic solvents cyclic esters γ-Butyrolactone 101.0 cyclic esters ε-caprolactone 115.0 Dialkyl ethers Diethylene glycol methyl ethyl ether 64.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 23.0 23.0 20.0 20.0 20.0 Dialkyl ethers Diethylene glycol diethyl ether 71.0 60.5 58.5 59.4 60.2 60.3 59.3 60.3 60.3 60.4 60.4 75.4 59.9 59.9 60.0 57.5 57.5 Dialkyl ethers Dipropylene glycol dimethyl ether 65.0 20.0 Monoalkyl ethers Dipropylene glycol monomethyl ether 76.5 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Monoalkyl ethers Diethylene glycol monobutyl ether 100.0 5.0 Monoalkyl ethers Triethylene glycol mono-n-butyl ether 156.0 Monoalkyl ethers Tetraethylene glycol monobutyl ether 166.0 Acetate Triethylene glycol mono-n-butyl ether acetate 290.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Acetate Diethylene glycol mono-n-butyl ether acetate 107.0 carbonates Propylene carbonate 135.0 lactates Ethyl lactate 52.0 Diester Diethyl oxalate 76.0 Cyclophenylamine 3-Methyl-2-azolidinone 115.0 alcohol 3-Methoxybutanol 62.5 Alkoxypropylamine N,N-Dimethyl-β-methoxypropionic acid 67.9 Resin acrylic resins Synthetic resin ① 1.0 acrylic resins Synthetic resin ② 0.5 0.5 0.1 1.0 0.5 0.5 0.5 0.5 0.5 Vinyl chloride-vinyl acetate copolymer resin Synthetic resin ① 0.1 0.1 Cellulose resin CAB-381-0.5 (Manufactured by Eastman Corporation) 0.1 0.1 Cellulose resin CAP-482-0.5 (Manufactured by Eastman Corporation) 0.1 Polyester resin Synthetic resins 0.1 Polyurethane resin Synthetic resins 0.1 dispersant Solsperse20000 (Manufactured by Lubrizol) 2.5 Solsperse33000 (Manufactured by Lubrizol) 2.5 additive Additive 1 (surfactants) UV3500 (Manufactured by BYK) Additive 2 (surfactants) BYK-331 (Manufactured by BYK) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 pigment Glossy Pigment 1 Synthetic product 1 Glossy Pigment 2 Synthetic product 2 1.0 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Glossy Pigment 3 Synthetic product 3 Glossy Pigment 4 Synthetic product 4 3.0 Glossy Pigment 5 Synthetic product 5 1.5 Glossy Pigment 6 Synthetic product 6 total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 evaluate Spreading 5 5 5 5 5 5 5 5 4 4 4 5 5 4 4 4 Surface drying properties 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Preservation stability 5 5 5 5 5 5 5 5 5 5 5 3 3 5 5 5 Ejection stability 5 3 5 5 5 5 5 5 4 4 4 5 5 5 5 5 Nozzle clogging evaluation 4 3 4 4 4 4 4 4 4 4 4 4 4 4 4 4 gloss 4 5 5 5 5 5 4 5 5 5 5 5 5 5 5 5 Cleaning and Restoration 5 3 5 5 5 5 5 5 5 5 5 5 5 5 5 5

[0260] [Table 10] Examples 2-43 Example 2-44 Example 2-45 Example 2-46 Example 2-47 Example 2-48 Example 2-49 Example 2-50 Example 2-51 Example 2-52 Examples 2-53 Example 2-54 Example 2-55 Example 2-56 Example 2-57 Example 2-58 Classification type name Flash point (°C) Organic solvent A Alkylamine solvents N,N-Dimethylformamide 58.0 Alkylamine solvents N,N-Diethylmethylamine 60.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 88.0 88.0 88.0 88.0 88.0 88.0 88.0 88.0 Alkylamine solvents N,N-Diethylpropionylamine 73.0 Alkylamine solvents N,N-Diethylacetamide 78.0 Cyclic amide solvents N-Methyl-ε-caprolactam 103.3 Cyclic amide solvents ε-caprolactam 125.0 Cyclic amide solvents N-Vinylcaprolactam 113.0 Cyclic amide solvents N-Methyl-2-pyrrolidone 86.1 Other organic solvents cyclic esters γ-Butyrolactone 101.0 10.0 10.0 cyclic esters ε-caprolactone 115.0 10.0 10.0 Dialkyl ethers Diethylene glycol methyl ethyl ether 64.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 Dialkyl ethers Diethylene glycol diethyl ether 71.0 50.0 50.0 50.0 50.0 50.0 50.0 50.0 50.0 Dialkyl ethers Dipropylene glycol dimethyl ether 65.0 Monoalkyl ethers Dipropylene glycol monomethyl ether 76.5 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Monoalkyl ethers Diethylene glycol monobutyl ether 100.0 Monoalkyl ethers Triethylene glycol mono-n-butyl ether 156.0 Monoalkyl ethers Tetraethylene glycol monobutyl ether 166.0 Acetate Triethylene glycol mono-n-butyl ether acetate 290.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Acetate Diethylene glycol mono-n-butyl ether acetate 107.0 carbonates Propylene carbonate 135.0 10.0 10.0 lactates Ethyl lactate 52.0 10.0 10.0 Diester Diethyl oxalate 76.0 10.0 10.0 Cyclophenylamine 3-Methyl-2-azolidinone 115.0 10.0 10.0 alcohol 3-Methoxybutanol 62.5 10.0 10.0 Alkoxypropylamine N,N-Dimethyl-β-methoxypropionic acid 67.9 10.0 10.0 Resin acrylic resins Synthetic resin① acrylic resins Synthetic resin ② 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Vinyl chloride-vinyl acetate copolymer resin Synthetic resin ① Cellulose resin CAB-381-0.5 (Manufactured by Eastman Corporation) Cellulose resin CAP-482-0.5 (Manufactured by Eastman Corporation) Polyester resin Synthetic resins Polyurethane resin Synthetic resins dispersant Solsperse20000 (Manufactured by Lubrizol) Solsperse33000 (Manufactured by Lubrizol) additive Additive 1 (surfactants) UV3500 (Manufactured by BYK) Additive 2 (surfactants) BYK-331 (Manufactured by BYK) pigment Glossy Pigment 1 Synthetic product 1 Glossy Pigment 2 Synthetic product 2 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Glossy Pigment 3 Synthetic product 3 Glossy Pigment 4 Synthetic product 4 Glossy Pigment 5 Synthetic product 5 Glossy Pigment 6 Synthetic product 6 total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 evaluate Spreading 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Surface drying properties 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Preservation stability 5 5 5 5 5 5 5 5 5 5 3 3 3 3 3 3 Ejection stability 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Nozzle clogging evaluation 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 gloss 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Cleaning and Restoration 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5

[0261] As shown in the table above, it can be seen that if the non-aqueous ink composition of the embodiment containing organic solvent A (selected from at least one of the group consisting of alkyl amide solvents (a1) and cyclic amide solvents (a2)) is a non-aqueous ink composition containing glossy pigments, it can also have both high cleanability and surface drying properties on the substrate.

[0262] Furthermore, it is known that when a glossy layer is formed from a non-aqueous ink composition containing an organic solvent A (selected from at least one of the group consisting of alkyl amide solvents (a1) and cyclic amide solvents (a2)), the gloss of the glossy layer can also be enhanced, giving it a good metallic sheen.

[0263] In particular, in the non-aqueous ink compositions of Examples 2-8 to 2-13, in which the content of organic solvent A (alkylamide solvent) was changed, especially in Examples 2-9 to 2-13 where the content of organic solvent A (alkylamide solvent) (a1) was in the range of 1% to 90% by mass, compared with Examples 2-8, records with higher cleanability and better surface drying properties were also obtained.

[0264] Furthermore, the non-aqueous ink compositions of Examples 2-1, 2-16 to 2-22, in which the type of organic solvent A is varied between alkyl amide solvents (a1) and cyclic amide solvents (a2), all exhibit the effects of the present invention.

[0265] Furthermore, in particular, the non-aqueous ink compositions of Examples 2-1, 2-23 to 2-27, which changed the volumetric cumulative particle size (D50) of the glossy pigment contained therein, also yielded records with higher cleanability and better surface drying properties compared to Example 2-28.

[0266] Furthermore, the non-aqueous ink compositions of Examples 2-30 to 2-34, which vary the type of resin contained, or the non-aqueous ink compositions of Examples 2-35 to 2-37, which do not contain resin, all achieve the effects of the present invention.

[0267] Furthermore, the non-aqueous ink compositions of Examples 2-45 to 2-50 and 2-53 to 2-58, which varied the type of organic solvent, all exhibited the effects of the present invention. Moreover, the non-aqueous ink compositions of Examples 2-53 to 2-58, which did not contain acetate-based solvents, showed a certain degree of decrease in storage stability. This confirms that non-aqueous ink compositions containing acetate-based solvents can improve the storage stability of non-aqueous ink compositions containing glossy pigments.

[0268] On the other hand, the non-aqueous ink compositions of Comparative Examples 2-1 to 2-6, which do not contain organic solvent A (selected from at least one of the group consisting of alkyl amide solvents (a1) and cyclic amide solvents (a2), have reduced surface drying properties and do not exert the effects of the present invention.

Claims

1. A non-aqueous ink composition comprising a colorant and an organic solvent, which is ejected by inkjet printing, wherein the colorant comprises a white pigment, and the organic solvent comprises an organic solvent A, wherein the content of the organic solvent A is 1.0% by mass or more and 90.0% by mass or less of the total amount of the non-aqueous ink composition, wherein the organic solvent A is selected from at least one of the group consisting of alkyl amide solvents (a1) and cyclic amide solvents (a2), wherein the alkyl amide solvent is represented by the following general formula (1), and the cyclic amide solvent comprises at least one of the group consisting of ε-caprolactone, N-methyl-ε-caprolactone and N-vinylcaprolactone, [Chemical 2] (in formula (1), R1 is hydrogen or an alkyl group having 1 to 4 carbon atoms, and R2 and R3 each independently represent an alkyl group having 2 to 4 carbon atoms).

2. The non-aqueous ink composition of claim 1, wherein the white pigment contains an inorganic oxide.

3. The non-aqueous ink composition of claim 2, wherein the white pigment contains titanium oxide.

4. The non-aqueous ink composition of any one of claims 1 to 3, wherein the content of the white pigment is more than 8% by mass and less than 20% by mass of the total amount of the non-aqueous ink composition.

5. The non-aqueous ink composition of any one of claims 1 to 3 further contains a surfactant, wherein the surfactant is a surfactant having a silicate skeleton, and the content of the surfactant having a silicate skeleton is more than 0.01% by mass and less than 1.0% by mass.

6. The non-aqueous ink composition of any one of claims 1 to 3 is used to form a base layer or top layer selected from the group consisting of black ink compositions, colored ink compositions, glossy ink compositions and transparent ink compositions.

7. A non-aqueous ink composition comprising a glossy pigment and an organic solvent, which is ejected by an inkjet method, wherein the organic solvent comprises an organic solvent A, wherein the content of the organic solvent A is 1.0% by mass or more and 90.0% by mass or less of the total amount of the non-aqueous ink composition, wherein the organic solvent A is selected from at least one of the group consisting of alkyl amide solvents (a1) and cyclic amide solvents (a2), wherein the alkyl amide solvent is represented by the following general formula (1), wherein the cyclic amide solvent comprises at least one of the group consisting of ε-caprolactam, N-methyl-ε-caprolactam and N-vinylcaprolactam, [Chemical 2] (in formula (1), R1 is hydrogen or an alkyl group having 1 to 4 carbon atoms, and R2 and R3 each independently represent an alkyl group having 2 to 4 carbon atoms).

8. The non-water-based ink composition of claim 7, wherein the glossy pigment contains a metallic glossy pigment.

9. The non-aqueous ink composition of claim 8, wherein the metal-containing glossy pigment comprises at least one selected from the group consisting of aluminum, aluminum alloys, indium, indium alloys, nickel, and nickel alloys.

10. The non-water-based ink composition of claim 9, wherein the aforementioned metal-containing glossy pigment contains at least aluminum or an aluminum alloy.

11. The non-aqueous ink composition of any one of claims 8 to 10, wherein the cumulative 50% particle size (D50) of the metal-containing glossy pigment is 0.01 μm or more and 5.0 μm or less, and the cumulative 90% particle size (D90) of the metal-containing glossy pigment is 10.0 μm or less.

12. The non-aqueous ink composition of any one of claims 8 to 10, wherein the aforementioned metal-containing glossy pigment is a particle having a flat surface.

13. The non-aqueous ink composition of claim 12, wherein the aforementioned metallic glossy pigment comprises a plate-like or flake-like metallic glossy pigment.

14. The non-aqueous ink composition of claim 13, wherein the thickness of the plate-like or flake-like metallic glossy pigment is in the range of 5 nm to 5.0 μm.

15. A non-aqueous ink composition according to any one of claims 7 to 10, wherein the organic solvent further comprises an acetate solvent represented by the following formula (2-3), [Chemical 1] (in formula (2-3), X1 is an alkyl group, X2 is hydrogen or alkyl; n represents an integer of 1 to 4).

16. The non-aqueous ink composition of any one of claims 7 to 10 is used to form a base layer or top layer selected from the group consisting of black ink compositions, colored ink compositions, glossy ink compositions and transparent ink compositions.

17. The non-aqueous ink composition of claim 1 or 7, wherein the organic solvent A contains the alkylamide solvent (a1).

18. The non-aqueous ink composition of claim 17, wherein the alkylamide solvent contains at least one selected from the group consisting of N,N-diethylmethylamine, N,N-diethylpropylamine and N,N-diethylacetamide.

19. The non-aqueous ink composition of claim 1 or 7, wherein the organic solvent A contains the cyclic amide solvent (a2).

20. The non-aqueous ink composition of claim 1 or 7, wherein the organic solvent further comprises at least one selected from the group consisting of glycol ether solvents, acetate solvents, cyclic esters, carbonates, diesters, lactates, amides and alcohols.

21. The non-aqueous ink composition of claim 1 or 7, wherein the organic solvent contains a glycol ether solvent.

22. The non-aqueous ink composition of claim 21, wherein the glycol ether solvent contains a glycol dialkyl ether.

23. The non-aqueous ink composition of claim 21, wherein the glycol ether solvent contains a glycol monoalkyl ether.

24. The non-aqueous ink composition of claim 21, wherein the glycol ether solvent contains at least two solvents with different flash points.

25. The non-aqueous ink composition of claim 1 or 7 further contains a resin.

26. The non-aqueous ink composition of claim 25, wherein the content of the resin is in the range of 0.1% by mass to 10.0% by mass of the total amount of the non-aqueous ink composition.

27. The non-aqueous ink composition of claim 25, wherein the resin contains at least one selected from the group consisting of acrylic resins, vinyl chloride resins, polyurethane resins, polyester resins and cellulose resins.

28. The non-aqueous ink composition of claim 25, wherein the non-aqueous ink composition is a white ink composition containing white pigment, and the content ratio of the resin to the white pigment is 0.20 to 1.

00.

29. An ink group comprising a non-aqueous ink composition as claimed in claim 1 or 7.

30. An ink assembly comprising a non-aqueous ink composition as claimed in claim 1 or 7, wherein the non-aqueous ink composition is a white ink composition containing a white pigment, wherein the non-aqueous ink composition and at least one of the group consisting of a black ink composition, a colored ink composition, a glossy ink composition and a transparent ink composition are simultaneously sprayed onto the surface of a substrate by inkjet.

31. An ink assembly comprising a non-aqueous ink composition as claimed in claim 1 or 7, wherein the non-aqueous ink composition is a glossy ink composition containing glossy pigments, and the non-aqueous ink composition, together with at least one selected from the group consisting of a black ink composition, a colored ink composition, a white ink composition, and a transparent ink composition, is simultaneously sprayed onto the surface of a substrate by inkjet.

32. A recording material formed by forming a recording layer of a non-aqueous ink composition as claimed in claim 1 or 7 on the surface of a substrate.

33. A recording method comprising inkjet printing a non-aqueous ink composition as claimed in claim 1 or 7 onto the surface of a substrate.

34. A method for manufacturing a recording, wherein a non-aqueous ink composition as claimed in claim 1 or 7 is sprayed onto the surface of a substrate by inkjet printing.

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