Non-aqueous ink composition, recording method using the same, and method for manufacturing a recording medium

Abstract

To provide a nonaqueous ink composition that can give a recorded matter having excellent surface dryability and excellent gloss.SOLUTION: A nonaqueous ink composition is ejected by the inkjet technique and contains an organic solvent, where the organic solvent contains an alkylamide solvent (a), and an organic solvent (b) with an enthalpy of evaporation (EOV) of 45 kJ / mol or more.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a non-aqueous ink composition, a recording method using the same, and a method for manufacturing a recording medium.

Background Art

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

[0003] For example, Patent Document 1 describes a technique related to a non-aqueous ink composition containing a cyclic ester (lactone-based solvent) and an organic solvent having a predetermined flash point. Patent Document 1 states that this non-aqueous ink composition contains a cyclic ester (lactone-based solvent) as a solvent, thereby dissolving a part of the recording surface and allowing the ink composition to penetrate into the interior of the recording medium, and improving the abrasion resistance of the image.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] Now, lactone-based solvents are solvents that easily penetrate resin substrates, and non-aqueous ink compositions containing lactone-based solvents have high permeability to resin substrates.

[0006] However, the inventors have found that when the non-aqueous ink composition penetrates into the resin substrate and the penetration amount increases, the glossiness and blocking resistance of the recording surface of the obtained recording material decrease. Further, when a predetermined low-volatile solvent is contained, although the volatilization of the organic solvent in the recording apparatus can be suppressed, the surface drying property of the recording material decreases. Then, it becomes difficult to improve the production speed of the recording material.

[0007] An object of the present invention is to provide a non-aqueous ink composition that is excellent in the surface drying property and blocking resistance of a recording material and can obtain a recording material having excellent glossiness.

Means for Solving the Problems

[0008] As a result of intensive studies to solve the above problems, the inventors have found that the above problems can be solved by a non-aqueous ink composition containing a predetermined organic solvent, and have completed the present invention. Specifically, the present invention provides the following.

[0009] (1) A non-aqueous ink composition containing an organic solvent and ejected by an inkjet method, wherein the organic solvent contains an alkylamide-based solvent (a) and an organic solvent (b) having an evaporation enthalpy (EOV) of 45 kJ / mol or more.

[0010] (2) The non-aqueous ink composition according to (1), wherein the organic solvent (b) contains at least one selected from the group consisting of glycol ether dialkyl, glycol ether monoalkyl, acetate, cyclic ester, carbonate, dibasic acid ester, lactate ester, amide, and alcohol.

[0011] (3) The non-aqueous ink composition according to (1) or (2), wherein the content of the organic solvent (b) is in the range of 1% by mass or more and 30% by mass or less in the total amount of the non-aqueous ink composition.

[0012] (4) The non-aqueous ink composition according to any one of (1) to (3), wherein the alkylamide-based solvent (a) is represented by the following general formula (1). [Chemical formula] (In formula (1), R1 is hydrogen or an alkyl group having 1 to 4 carbon atoms, and R2 and R3 each independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms.)

[0013] (5) The non-aqueous ink composition according to (4), wherein the alkylamide-based solvent (a) contains at least one selected from the group consisting of N,N-diethylformamide, N,N-diethylpropanamide, and N,N-diethylacetamide.

[0014] (6) The non-aqueous ink composition according to any one of (1) to (5), wherein the content of the alkylamide-based solvent (a) is in the range of 1% by mass or more and 90% by mass or less in the total amount of the non-aqueous ink composition.

[0015] (7) The non-aqueous ink composition according to any one of (1) to (6), further containing a resin, wherein the resin having an intrinsic viscosity of 90 mL / g or more at 25°C is in the range of 5% by mass or less in the total amount of the resin.

[0016] (8) The non-aqueous ink composition according to any one of (1) to (7), which is ejected by an inkjet method using an inkjet recording apparatus including a heating mechanism and a fixing mechanism for fixing a substrate.

[0017] (9) The non-aqueous ink composition according to any one of (1) to (8), which is ejected by an inkjet method through a plastic tube using an inkjet recording apparatus including a plastic tube.

[0018] (10) A recording method of ejecting the non-aqueous ink composition according to any one of (1) to (9) onto the surface of a substrate by an inkjet method.

[0019] (11) A method for manufacturing a recorded product of ejecting the non-aqueous ink composition according to any one of (1) to (9) onto the surface of a substrate by an inkjet method.

[0020] (12) A recording medium in which a recording layer of the non-aqueous ink composition according to any one of (1) to (9) is formed on the surface of a substrate.

Advantages of the Invention

[0021] Even when the non-aqueous ink composition of the present invention contains a low-volatility solvent, it is excellent in surface dryness and blocking resistance of the recording medium, and a recording medium having excellent glossiness can be obtained.

Embodiments for Carrying Out the Invention

[0022] Hereinafter, specific embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within the scope of the object of the present invention. In addition, in this specification, the notation "~" means "above" and "below", the notation "X:Y~A:B" includes "X:Y" and "A:B" themselves, and means the range between "X:Y" and "A:B".

[0023] <1. Non-aqueous Ink Composition> The non-aqueous ink composition according to the present embodiment contains an organic solvent and is a non-aqueous ink composition ejected by an inkjet method. As the organic solvent, it contains an alkylamide-based solvent (a) and an organic solvent (b) having an evaporation enthalpy (EOV) of 45 kJ / mol or more.

[0024] Such a non-aqueous ink composition is excellent in surface dryness and blocking resistance of the recording medium, and a recording medium having excellent glossiness can be obtained.

[0025] Here, the "non-aqueous ink composition" means an ink composition (oil-based ink composition) that does not contain water, and is different from an aqueous ink composition in which a coloring material is dissolved or dispersed in water or a mixed liquid of water and an organic solvent. In addition, in this specification, the phrase "does not contain water" does not consider water that is inevitably contained such as moisture in the air or water derived from additives.

[0026] Note that the non-aqueous ink composition according to this embodiment may be a colored ink containing a coloring material (including a colored coloring material or a black-and-white coloring material), an ink containing a glitter pigment (scaly metal particles) for making a recording object (substrate) metallic, or a clear ink containing no coloring material. When it is a clear ink containing no coloring material, examples of the ink include an overcoat ink composition for forming a layer having a desired function, a matting ink composition for dulling the luster of a recording object (substrate), and an ink containing an ultraviolet absorber, a light stabilizer, etc. for forming a weather-resistant layer.

[0027] Hereinafter, each component contained in the non-aqueous ink composition according to this embodiment will be described.

[0028] [Organic solvent] The organic solvent contains an alkylamide-based solvent (a) and an organic solvent (b) having an evaporation enthalpy (EOV) of 45 kJ / mol or more.

[0029] (Alkylamide-based solvent (a)) The alkylamide-based solvent is a compound having an alkyl group (C n H 2n+1 -) and a -C(=O)-N- group (amide bond), and is an organic solvent composed of a compound composed of a hydrogen or an alkyl group and a -C(=O)-N- group.

[0030] The alkylamide-based solvent (a) is a solvent that penetrates the substrate to some extent in the same manner as the lactone-based solvent. And the alkylamide-based solvent (a) has higher volatility than the lactone-based solvent, and as a result, the amount of penetration into the substrate can be made lower than that of the non-aqueous ink composition containing the lactone-based solvent. For this reason, it is possible to improve the glossiness of the recording surface of the obtained recording object while enjoying the benefits of the non-aqueous ink composition containing the lactone-based solvent.

[0031] In addition, since the alkylamide-based solvent (a) is easy to dry, a non-aqueous ink composition containing the alkylamide-based solvent (a) can obtain a recording material with excellent surface drying properties even if it contains the organic solvent (b) described later. Furthermore, the non-aqueous ink composition landing on the base material (recording medium) has high drying properties, less bleeding of printing, and clear printing. Moreover, for a non-aqueous ink composition containing the alkylamide-based solvent (a) which is easier to dry than the lactone-based solvent, the permeability to the base material is reduced to some extent as described above, and the amount of solvent remaining in the base material after surface drying is reduced. Thereby, the occurrence of blocking can be suppressed, and the member suitability for the inkjet recording apparatus is also improved.

[0032] The alkylamide-based solvent is preferably an organic solvent composed only of a hydrogen or alkyl group and a -C(=O)-N- group without containing an alkoxy group, for example. For example, those having the following structure can be preferably used.

[0033] [Chemical formula] (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.)

[0034] In addition, 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.

[0035] Examples of the alkylamide solvents include N,N - diethylformamide, N,N - diethylacetamide, N,N - dipropylformamide, N,N - dibutylformamide, N,N - diethylpropanamide, N,N - dipropylpropanamide, N - ethylformamide, N - ethylacetamide, and the like. Among these, from the viewpoint of particularly exhibiting the effects of the present invention, it is preferable to contain at least one selected from the group consisting of N,N - diethylformamide, N,N - diethylpropanamide, and N,N - diethylacetamide, and among these, it is particularly preferable to contain N,N - diethylformamide.

[0036] The content of the alkylamide solvent (a) is not particularly limited, but the lower limit of the content of the alkylamide solvent (a) is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably in the range of 5% by mass or more, still more preferably in the range of 10% by mass or more, and even more preferably in the range of 15% by mass or more in the total amount of the non - aqueous ink composition. Thereby, a recording material with more excellent surface dryness can be obtained, the bleeding of printing is further reduced, and the printing becomes clearer.

[0037] The upper limit of the content of the alkylamide solvent (a) is preferably in the range of 90% by mass or less, more preferably in the range of 70% by mass or less, still more preferably 60% by mass or less, still more preferably 50% by mass or less, and even more preferably in the range of 45% by mass or less in the total amount of the non - aqueous ink composition. Thereby, a non - aqueous ink composition capable of obtaining a recording material showing more excellent glossiness can be obtained.

[0038] (Organic solvent (b)) The organic solvent (b) is an organic solvent having an evaporation enthalpy (EOV) of 45 kJ / mol or more. In this specification, the evaporation enthalpy is a calculated value determined using Advanced Chemistry Development (ACD / Labs) software, version 11.02.

[0039] The higher the value of this evaporation enthalpy, the more difficult it is for the organic solvent to volatilize. It means that an organic solvent (b) with an evaporation enthalpy (EOV) of 45 kJ / mol or more is a low-volatility solvent with low volatility.

[0040] By containing such an organic solvent (b) with an evaporation enthalpy (EOV) of 45 kJ / mol or more, the permeability of the alkylamide-based solvent (a) contained in the non-aqueous ink composition to the substrate can be reduced, and a recording material showing excellent glossiness can be obtained. Furthermore, since the volatilization of the non-aqueous ink composition can be suppressed until the non-aqueous ink composition lands on the substrate (recording medium), the maintainability is excellent, and the inkjet ejection property of the non-aqueous ink composition is also improved. Incidentally, the evaporation enthalpy (EOV) of this organic solvent (b) is preferably 45.5 kJ / mol or more, more preferably 46.0 kJ / mol or more. Also, the upper limit of the evaporation enthalpy (EOV) of this organic solvent (b) is not particularly limited, but is preferably 90 kJ / mol or less, more preferably 80 kJ / mol or less, and even more preferably 70 kJ / mol or less.

[0041] The type of the organic solvent (b) having an evaporation enthalpy (EOV) of 45 kJ / mol or more is not particularly limited, but it is preferably a glycol ether dialkyl, a glycol ether monoalkyl, an acetate, a cyclic ester, a carbonate ester, a dibasic acid ester, a lactate ester, an amide, or an alcohol, and more preferably an organic solvent having an evaporation enthalpy (EOV) of 45 kJ / mol or more, which is a glycol ether dialkyl, a glycol ether monoalkyl, an acetate, a carbonate ester, a dibasic acid ester, or a lactate ester, and still more preferably an organic solvent having an evaporation enthalpy (EOV) of 45 kJ / mol or more, which is a glycol ether dialkyl, a glycol ether monoalkyl, or a carbonate ester. Thereby, it becomes possible to achieve a good balance between the surface dryness and glossiness of the recorded matter.

[0042] Examples of the glycol ether dialkyl include diethylene glycol dibutyl ether (47.2 kJ / mol), tetraethylene glycol dimethyl ether (49.3 kJ / mol), tetraethylene glycol diethyl ether (51.9 kJ / mol), and the like.

[0043] Examples of glycol ether monoalkyls include diethylene glycol monomethyl ether (50.1 kJ / mol), diethylene glycol monoethyl ether (51.0 kJ / mol), diethylene glycol mono-n-butyl ether (54.3 kJ / mol), triethylene glycol monomethyl ether (54.7 kJ / mol), triethylene glycol mono-n-butyl ether (60.0 kJ / mol), tetraethylene glycol monobutyl ether (66.9 kJ / mol), pentaethylene glycol monobutyl ether (72.4 kJ / mol), hexaethylene glycol monobutyl ether (77.6 kJ / mol), dipropylene glycol monomethyl ether (51.1 kJ / mol), dipropylene glycol monopropyl ether (55.8 kJ / mol), tripropylene glycol monomethyl ether (59.1 kJ / mol), and the like.

[0044] Examples of acetates include diethylene glycol mono-n-butyl ether acetate (48.2 kJ / mol), diethylene glycol mono-n-ethyl ether acetate (45.8 kJ / mol), and the like.

[0045] Examples of cyclic esters include ε-caprolactone (46.2 kJ / mol), δ-valerolactone (45.4 kJ / mol), δ-hexanolactone (45.2 kJ / mol), and the like.

[0046] Examples of carbonates include propylene carbonate (47.8 kJ / mol), ethylene carbonate (49.0 kJ / mol).

[0047] Examples of dibasic acid esters include dipropyl malonate (46.6 kJ / mol), diethyl succinate (45.5 kJ / mol), diethyl glutarate (47.3 kJ / mol), dimethyl adipate (46.5 kJ / mol), and the like.

[0048] Examples of the lactate esters include ethyl lactate (45.6 kJ / mol), butyl lactate (49.5 kJ / mol), propyl lactate (47.8 kJ / mol), ethylhexyl lactate (55.8 kJ / mol), amyl lactate (51.3 kJ / mol), isoamyl lactate (51.0 kJ / mol), and the like.

[0049] Examples of the amides include 3-methyl-2-oxazolidinone (50.4 kJ / mol), 3-ethyl-2-oxazolidinone (50.7 kJ / mol), N-methylcaprolactam (48.5 kJ / mol), N-acetylcaprolactam (47.9 kJ / mol), ε-caprolactam (51.1 kJ / mol), N-vinylcaprolactam (49.2 kJ / mol), N,N-dimethyl-β-butoxypropionamide (48.5 kJ / mol), and the like.

[0050] Examples of the alcohols include 3-methoxybutanol (46.5 kJ / mol), 3-methoxy-3-methylbutanol (46.7 kJ / mol), diacetone alcohol (47.1 kJ / mol), and the like.

[0051] Examples of the organic solvents (b) other than glycol ether dialkyl, glycol ether monoalkyl, acetate, cyclic ester, carbonate ester, dibasic acid ester, lactate ester, amide, and alcohol include hydroxy acid esters. Examples of the hydroxy acid esters include triethyl citrate (61.9 kJ / mol), and the like.

[0052] The content of the organic solvent (b) with an evaporation enthalpy (EOV) of 45 kJ / mol or more is not particularly limited, but the lower limit of the content of the organic solvent (b) is preferably in the range of 1% by mass or more, more preferably in the range of 3% by mass or more, and even more preferably in the range of 5% by mass or more in the total amount of the non-aqueous ink composition. Thereby, the permeability of the alkylamide-based solvent (a) contained in the non-aqueous ink composition to the substrate can be reduced, and a recording material exhibiting more excellent glossiness can be obtained. The upper limit of the content of the organic solvent (b) is preferably in the range of 30% by mass or less, more preferably in the range of 20% by mass or less, and even more preferably in the range of 15% by mass or less in the total amount of the non-aqueous ink composition. Thereby, a recording material having more excellent surface drying property can be obtained.

[0053] (Other organic solvents) The organic solvent may contain an organic solvent other than the above alkylamide-based solvent (a) and the organic solvent (b) with an evaporation enthalpy (EOV) of 45 kJ / mol or more. Specifically, different from the alkylamide-based solvent, an organic solvent with an evaporation enthalpy (EOV) of less than 45 kJ / mol can be mentioned.

[0054] For example, glycol ether dialkyl, glycol ether monoalkyl, acetate, cyclic ester, amide different from the above alkylamide-based solvent (a), lactate ester, dibasic acid ester, etc. with an evaporation enthalpy (EOV) of less than 45 kJ / mol can be mentioned.

[0055] Examples of the glycol ether dialkyl with an evaporation enthalpy (EOV) of less than 45 kJ / mol include diethylene glycol dimethyl ether (38.0 kJ / mol), diethylene glycol methyl ethyl ether (38.8 kJ / mol), diethylene glycol diethyl ether (40.9 kJ / mol), diethylene glycol isopropyl methyl ether (40.4 kJ / mol), triethylene glycol dimethyl ether (43.4 kJ / mol), and dipropylene glycol dimethyl ether (39.8 kJ / mol).

[0056] As the monoalkyl ether with an evaporation enthalpy (EOV) of less than 45 kJ / mol, there are ethylene glycol monomethyl ether (37.5 kJ / mol), ethylene glycol monoethyl ether (39.2 kJ / mol), ethylene glycol monopropyl ether (44.89 kJ / mol), propylene glycol monomethyl ether (41.6 kJ / mol), propylene glycol monoethyl ether (43.0 kJ / mol).

[0057] As the acetate with an evaporation enthalpy (EOV) of less than 45 kJ / mol, there are ethylene glycol monobutyl ether acetate (42.8 kJ / mol), propylene glycol monomethyl ether acetate (39.2 kJ / mol), 2-methylbutyl acetate (37.3 kJ / mol), 3-methoxybutyl ether acetate (41.2 kJ / mol), cyclohexyl acetate (40.9 kJ / mol).

[0058] As the cyclic ester with an evaporation enthalpy (EOV) of less than 45 kJ / mol, there are γ-butyrolactone (44.0 kJ / mol), γ-valerolactone (44.3 kJ / mol).

[0059] As the amide with an evaporation enthalpy (EOV) of less than 45 kJ / mol, there are N,N-dimethyl-β-methoxypropionamide (42.5 kJ / mol), N-vinylmethyloxazolidinone (38.3 kJ / mol).

[0060] As the lactate ester with an evaporation enthalpy (EOV) of less than 45 kJ / mol, there is methyl lactate (44.5 kJ / mol).

[0061] As the dibasic acid ester with an evaporation enthalpy (EOV) of less than 45 kJ / mol, there are dimethyl malonate (41.3 kJ / mol), diethyl malonate (43.6 kJ / mol), dipropyl malonate (46.6 kJ / mol), dimethyl succinate (43.2 kJ / mol).

[0062] Moreover, it may contain organic solvents other than the above-mentioned organic solvents. Specifically, alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, etc., ketones such as acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl isopropyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, methyl-n-amyl ketone, methyl hexyl ketone, methyl isoamyl ketone, diethyl ketone, ethyl-n-propyl ketone, ethyl isopropyl ketone, ethyl-n-butyl ketone, ethyl isobutyl ketone, di-n-propyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, isophorone, acetyl ketone, etc., acetic acid esters such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, octyl acetate, etc., glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, etc., saturated hydrocarbons such as n-hexane, isohexane, n-nonane, isononane, dodecane, isododecane, etc., unsaturated hydrocarbons such as 1-hexene, 1-heptene, 1-octene, etc., cyclic saturated hydrocarbons such as cyclohexane, cycloheptane, cyclooctane, cyclodecane, decalin, etc., cyclic unsaturated hydrocarbons such as cyclohexene, cycloheptene, cyclooctene, 1,1,3,5,7-cyclooctatetraene, cyclododecene, etc., aromatic hydrocarbons such as benzene, toluene, xylene, etc., morpholines such as N-methylmorpholine, N-ethylmorpholine, N-formylmorpholine, terpene solvents, and ether solvents, etc. General organic solvents can be listed regardless of the evaporation enthalpy (EOV). It is preferable to select a solvent with an appropriate HLB value according to the resin, dispersant, etc. to be combined.

[0063] Incidentally, the non-aqueous ink composition according to the present embodiment may contain a lactone-based solvent having an evaporation enthalpy (EOV) of less than 45 kJ / mol. However, if a large amount of the lactone-based solvent is contained, the effect of the present invention of obtaining a recording material exhibiting excellent glossiness may not be obtained. The content of the lactone-based solvent having an evaporation enthalpy (EOV) of less than 45 kJ / mol is preferably in the range of 5.0% by mass or less, more preferably in the range of 3.0% by mass or less, still more preferably in the range of 1.0% by mass or less, and even more preferably in the range of 0.1% by mass or less in the total amount of the non-aqueous ink composition.

[0064] The content of other organic solvents is not particularly limited. However, the lower limit of the content of other organic solvents is preferably in the range of 10% by mass or more, more preferably in the range of 20% by mass or more, and still more preferably in the range of 30% by mass or more. The upper limit of the content of other organic solvents is preferably in the range of 85% by mass or less, more preferably in the range of 80% by mass or less, and still more preferably in the range of 75% by mass or less.

[0065] [Resin] The non-aqueous ink composition according to the present embodiment may not contain a resin, but may contain a resin. By containing a resin, the fixability, water resistance, and stretchability of the recording layer formed by the non-aqueous ink composition can be improved. Furthermore, the glossiness of the obtained recording material can be more effectively improved. These resins are so-called binder resins that form a coating film (recording layer) and are distinguished from polymer dispersants that disperse color materials (pigments).

[0066] The resin is not particularly limited. 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, vinyl toluene-α-methylstyrene copolymers, ethylene-vinyl acetate copolymers, cellulose resins, silicone resins, acrylamide resins, epoxy resins, or copolymer resins or mixtures thereof can be used. Among these, those containing acrylic resins, vinyl chloride-vinyl acetate copolymer resins, cellulose resins, polyester resins, or polyurethane resins are preferred.

[0067] The acrylic resin is not particularly limited as long as it contains, as the main component of the monomers constituting the (meth)acrylic acid ester monomer. The acrylic resin may be a homopolymer of one radical-polymerizable monomer or any copolymer obtained by selecting and using two or more radical-polymerizable monomers. In particular, the acrylic resin preferred as the oil-based ink composition according to the present embodiment is a polymer of methyl methacrylate alone, or a copolymer of methyl methacrylate and at least one compound selected from the group consisting of butyl methacrylate, ethoxyethyl methacrylate, and benzyl methacrylate. Examples of commercially available (meth)acrylic resins include "Paraloid B99N", "Paraloid B60", "Paraloid B66", "Paraloid B82", etc. of Rohm and Haas.

[0068] The vinyl chloride-vinyl acetate copolymer resin is a polymer of vinyl chloride monomer and vinyl acetate monomer. Examples of vinyl chloride-vinyl acetate copolymer resins include vinyl chloride-vinyl acetate copolymer, vinyl chloride / vinyl acetate / maleic acid copolymer, vinyl chloride / vinyl acetate / vinyl alcohol copolymer, vinyl chloride / vinyl acetate / hydroxyalkyl acrylate copolymer, etc., and mixtures thereof. As the above vinyl chloride-vinyl acetate copolymer resin, it can be obtained under the trade names of Solvaine C, CL, CNL, CLL, CLL2, C5R, TA2, TA3, A, AL, TA5R, M5, etc. from Nissin Chemical Industry Co., Ltd. and used in the present invention.

[0069] The vinyl chloride-vinyl acetate copolymer resin can be obtained by polymerizing vinyl chloride monomer and vinyl acetate monomer. Any conventionally known polymerization method may be used. The polymerization method is preferably emulsion polymerization or suspension polymerization, and more preferably suspension polymerization.

[0070] The cellulose-based resin is a resin having a cellulose skeleton obtained by introducing functional groups biologically or chemically using cellulose as a raw material. For example, examples of cellulose-based resins include cellulose acetate alkylate resins such as cellulose acetate butyrate resin, cellulose acetate propionate resin, cellulose acetate propionate butyrate resin, cellulose acetate resin, nitrocellulose resin, and mixtures thereof. As the above cellulose resin, it can be obtained and used under the trade names of "CAB551-0.01", "CAB551-0.2", "CAB553-0.4", "CAB531-1", "CAB381-0.1", "CAB381-0.5", "CAB381-2", "CAB381-20", "CAP504", "CAP482-0.5", etc. from EASTMAN.

[0071] The polyester resin is at least composed of structural units obtained by polycondensing an alcohol component and a carboxylic acid component. The polyester resin may include a modified polyester resin. As the above polyester resin, it can be obtained and used under the trade names such as “VYLON226”, “VYLON270”, “VYLON560”, “VYLON600”, “VYLON630”, “VYLON660”, “VYLON885”, “VYLONGK250”, “VYLONGK810”, “VYLON GK890” of Toyobo Co., Ltd. and “elitleUE-3200”, “elitleUE-3285”, “elitleUE-3320”, “elitleUE-9800”, “elitleUE-9885” of Unitika Ltd.

[0072] The polyurethane resin is at least composed of structural units obtained by copolymerizing an alcohol component and an isocyanate component. The polyurethane resin may include a polyurethane resin modified with polyester, polyether, or caprolactone. As the above polyurethane resin, it can be obtained and used under the trade names such as “Yureano KL-424”, “Yureano KL-564”, “Yureano KL-593”, “Yureano 3262” of Arakawa Chemical Industries, Ltd. and “Pandex 372E”, “Pandex 390E”, “Pandex 394E”, “Pandex 304”, “Pandex 305E”, “Pandex P-870”, “Pandex P-910”, “Pandex P-895”, “Pandex 4030”, “Pandex 4110” of DIC Corporation.

[0073] In addition, these acrylic resins, vinyl chloride-vinyl acetate copolymer resins, cellulose resins, polyester resins, and polyurethane resins may be used alone, but it is preferable to use them as a mixture of two types, and it is more preferable to use a resin obtained by mixing an acrylic resin and a vinyl chloride-vinyl acetate copolymer resin. By adjusting the content ratio of the acrylic resin and the vinyl chloride-vinyl acetate copolymer resin, it is possible to control the ink so as to meet the requirements such as color development, drying property, coating film physical properties, and printing suitability required for the non-aqueous ink. When mixing an acrylic resin and a vinyl chloride-vinyl acetate copolymer resin, the mixing ratio is not particularly limited and can be appropriately changed.

[0074] The weight average molecular weight (relative molecular mass) of the resin is not particularly limited, but is preferably 5,000 or more, and more preferably 15,000 or more. The weight average molecular weight (relative molecular mass) is preferably 100,000 or less, and more preferably 50,000 or less. The relative molecular weight of the resin can be measured by ordinary GPC (gel permeation chromatography).

[0075] The resin contained in the non-aqueous ink composition is preferably contained in the range of 0.05% by mass or more, more preferably in the range of 0.1% by mass or more, and even more preferably in the range of 0.5% by mass or more based on the total amount of the non-aqueous ink composition. The resin contained in the non-aqueous ink composition is preferably contained in the range of 20.0% by mass or less, more preferably in the range of 15.0% by mass or less, and even more preferably in the range of 10.0% by mass or less based on the total amount of the non-aqueous ink composition.

[0076] In addition, in the resin contained in the non-aqueous ink composition according to the present embodiment, it is preferable that the resin having an intrinsic viscosity of 90 mL / g or more at 25°C is in the range of 5% by mass or less based on the total amount of the resin. Thereby, the printing performance such as continuous discharge stability is excellent, and the glossiness of the obtained recording material can be more effectively improved.

[0077] In this specification, the intrinsic viscosity is the specific viscosity [η SP ((η - η0) / η0 (η0: solvent viscosity, η: solution viscosity)) and the concentration C are obtained after separating the molecules contained in the resin by a column filled with granular gel in GPC (gel permeation chromatography) by dispersing the target resin in a developing solvent, and in the formula Lim([[η SP / C), it can be obtained by extrapolating the concentration C to 0 (C → 0). The developing solvent is not particularly limited, and for example, tetrahydrofuran can be used.

[0078] Note that the content of the resin having an intrinsic viscosity of 90 mL / g or more at 25°C is preferably 4.0% by mass or less, more preferably 3.5% by mass or less, and even more preferably 2.5% by mass or less in the total amount of the resin.

[0079] [Colorant] The non-aqueous ink composition according to this embodiment may contain a colorant. The colorant is not particularly limited, and may be a dye-based or a pigment-based one. However, from the viewpoint of good resistance such as water resistance and light resistance of the recorded matter, it is preferable to use a pigment (pigment-based colorant). In the non-aqueous ink composition according to this embodiment, the pigments that can be used are not particularly limited, and examples include organic pigments or inorganic pigments used in conventional ink compositions. These may be used alone or in combination of two or more. Note that the non-aqueous ink composition according to this embodiment may not contain a colorant.

[0080] When a pigment is used in the non-aqueous ink composition according to this embodiment, the dispersion stability of the pigment can be improved by using a dispersant or a dispersion aid (pigment derivative) described later.

[0081] Specific organic pigments include, for example, insoluble azo pigments, soluble azo pigments, derivatives from dyes, phthalocyanine-based organic pigments, quinacridone-based organic pigments, perylene-based organic pigments, perinone-based organic pigments, azomethine-based organic pigments, anthraquinone-based organic pigments (anthrone-based organic pigments), xanthene-based organic pigments, diketopyrrolopyrrole-based organic pigments, dioxazine-based organic pigments, nickel azo pigments, isoindolinone-based organic pigments, pyranthrone-based organic pigments, thioindigo-based organic pigments, condensed azo-based organic pigments, benzimidazolone-based organic pigments, quinophthalone-based organic pigments, isoindoline-based organic pigments, quinacridone-based solid solution pigments, perylene-based solid solution pigments and other organic solid solution pigments, and other pigments such as lake pigments and carbon black.

[0082] Illustrating the organic pigments by Color Index (C.I.) numbers, there may be mentioned C.I. Pigment Yellow 1, 2, 3, 12, 13, 14, 16, 17, 20, 24, 73, 74, 75, 83, 93, 95, 97, 98, 109, 110, 114, 117, 120, 125, 128, 129, 130, 137, 138, 139, 147, 148, 150, 151, 153, 154, 155, 166, 168, 180, 185, 213, 214, C.I. Pigment Red 5, 7, 9, 12, 48, 49, 52, 53, 57:1, 97, 112, 122, 123, 146, 149, 150, 168, 177, 180, 184, 192, 202, 206, 208, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 238, 240, 254, 255, 269, 291, C.I. Pigment Orange 16, 36, 43, 51, 55, 59, 61, 64, 71, 73, C.I. Pigment Violet 19, 23, 29, 30, 37, 40, 50, C.I. Pigment Blue 15, 15:1, 15:3, 15:4, 15:6, 16, 22, 60, 64, C.I. Pigment Green 7, 36, 58, 59, 62, 63, C.I. Pigment Brown 23, 25, 26, C.I. Pigment Black 7, etc.

[0083] In the non-aqueous ink composition according to the present embodiment, specific examples of dyes that can be used include azo dyes, benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, cyanine dyes, squarylium dyes, croconium dyes, merocyanine dyes, stilbene dyes, diarylmethane dyes, triarylmethane dyes, fluoran dyes, spiropyran dyes, phthalocyanine dyes, indigo dyes such as indigoid, fulgide dyes, nickel complex dyes, and azulene dyes.

[0084] In the non-aqueous ink composition according to the present embodiment, specific examples of inorganic pigments that can be used include titanium oxide, barium sulfate, calcium carbonate, zinc oxide, barium carbonate, silica, talc, clay, synthetic mica, alumina, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine blue, dark blue, chromium oxide green, cobalt green, amber, titanium black, aluminum, titanium, indium, synthetic iron black, inorganic solid solution pigments, and the like.

[0085] In the non-aqueous ink composition according to this embodiment, the average dispersed particle diameter of the pigment that can be contained is not particularly limited as long as it enables a desired color development. Although it varies depending on the type of pigment used, from the viewpoint of good dispersibility and dispersion stability of the pigment and obtaining sufficient coloring power, it is preferably within a range of 5 nm or more, more preferably 20 nm or more, and even more preferably 30 nm or more in terms of volume average particle diameter. By having the volume average particle diameter be equal to or greater than the above lower limit value, the light resistance of the non-aqueous ink composition can be improved. It is preferably within a range of 300 nm or less, more preferably 200 nm or less, and even more preferably 150 nm or less in terms of volume average particle diameter. By having the volume average particle diameter be equal to or less than the above upper limit value, when the non-aqueous ink composition is a non-aqueous inkjet ink composition that is ejected onto the surface of a substrate by an inkjet method, the ejection stability of the inkjet can be improved. In this embodiment, the volume average particle diameter of the pigment is the volume average particle diameter (D50) measured under the condition of 25°C using a particle size distribution measuring device (particle size analyzer NANOTRAC WAVE manufactured by Microtrac Bell Co., Ltd.).

[0086] Further, in an ink set including a plurality of non-aqueous ink compositions according to this embodiment, the volume average particle diameters of the pigments contained in the respective non-aqueous ink compositions may be the same or may be different. For example, in the case of an ink set including a cyan ink and a magenta ink of the non-aqueous ink composition according to this embodiment, the volume average particle diameter of the pigment contained in the cyan ink and the volume average particle diameter of the pigment contained in the magenta ink may be the same or may be different.

[0087] In the non-aqueous ink composition according to this embodiment, the content of the pigment is not particularly limited as long as a desired image can be formed, and is appropriately adjusted. Specifically, although it varies depending on the type of pigment, it is preferably 0.05% by mass or more, more preferably 0.1% by mass or more in the total amount of the non-aqueous ink composition. It is preferably 20% by mass or less, more preferably 10% by mass or less in the total amount of the non-aqueous ink composition. By the content of the pigment being within the range of 0.05% by mass or more and 20% by mass or less, it is possible to obtain an excellent balance between the dispersion stability of the pigment and the coloring power.

[0088] Also, the color to be recorded (printed) by the non-aqueous ink composition according to this embodiment is not particularly limited, and color materials may be selected and used in combination according to the color for the purpose. The color can also be used for inks of various colors such as yellow, magenta, cyan, black, and also for light magenta, light cyan, light black, orange, green, red, white, etc. At this time, in the ink set containing the non-aqueous ink composition according to this embodiment, color materials of the same type of color may be selected.

[0089] [Dispersant] In the non-aqueous ink composition according to this embodiment, a dispersant may be used as needed. As the dispersant, any dispersant used in the non-aqueous ink composition can be used. It is preferable to use a polymer dispersant as the dispersant. Such dispersants have a main chain composed of polyester-based, polyacrylic-based, polyurethane-based, polyamine-based, polycaprolactone-based, etc., and have polar groups such as amino groups, carboxyl groups, sulfonic groups, and hydroxyl groups as side chains. In the case of polyacrylic-based dispersants, for example, Disperbyk-2000, 2001, 2008, 2009, 2010, 2020, 2020N, 2022, 2025, 2050, 2070, 2095, 2150, 2151, 2155, 2163, 2164, BYKJET-9130, 9131, 9132, 9133, 9151 (manufactured by BYK-Chemie GmbH), Efka PX4310, PX4320, PX4330, PA4401, 4402, PA4403, 4570, 7411, 7477, PX4700, PX4701 (manufactured by BASF SE), 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. are used. In the case of polycaprolactone-based dispersants, for example, Ajisper PB821, PB822, PB881 (manufactured by Ajinomoto Fine-Techno Co., Inc.), Hinact KF-1000, T-6000, T-7000, T-8000, T-8000E, T-9050 (manufactured by Kawaken Fine Chemicals 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 Corporation), TEGO Dispers 652, 655, 685, 688, 690 (manufactured by Evonik Japan Co., Ltd.), etc. are used.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, TEGO Dispers 655, 685, 688, 690, etc. These can be used alone or as mixtures thereof.

[0090] The content of the dispersant is not particularly limited. However, the lower limit of the content of the dispersant is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 0.8% by mass or more in the total amount of the non-aqueous ink composition. The content of the dispersant is not particularly limited. However, the upper limit of the content of the dispersant is preferably 5.0% by mass or less, more preferably 4.0% by mass or less, and even more preferably 3.0% by mass or less in the total amount of the non-aqueous ink composition.

[0091] [Dispersing aid] In the non-aqueous ink composition according to this embodiment, a dispersing aid may be used as needed. The dispersing aid adsorbs on the surface of the coloring material (pigment), and the functional groups enhance the affinity with the organic solvent and the dispersant in the non-aqueous ink composition, improving the dispersion stability. As the dispersing aid, known pigment derivatives having functional groups such as acidic groups, basic groups, and neutral groups on the organic pigment residue can be used.

[0092] [Surfactant] In the non-aqueous ink composition according to this embodiment, for the purpose of suppressing the volatilization, preventing solidification, and improving the redissolvability when solidified of the non-aqueous ink composition in equipment such as the nozzle part and inside the tube, and also for the purpose of reducing the surface tension and improving the wettability with the recording medium (base material), a surfactant may be added. For example, nonionic P-208, P-210, P-213, E-202S, E-205S, E-215, K-204, K-220, S-207, S-215, A-10R, A-13P, NC-203, NC-207 (manufactured by NOF Corporation), Emulgen 106, 108, 707, 709, A-90, A-60 (manufactured by Kao Corporation), Floren G-70, D-90, TG-740W (manufactured by Kyoeisha Chemical Co., Ltd.), POEM J-0081HV (manufactured by Riken Vitamin Co., Ltd.), Adeka Tol NP-620, NP-650, NP-660, NP-675, NP-683, NP-686, Adeka Cole CS-141E, TS-230E (manufactured by ADEKA Corporation), etc., Sorgen 30V, 40, TW-20, TW-80, Neugen CX-100 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), etc. As the fluorine-based surfactant, it is preferable to use a fluorine-modified polymer. Specific examples include BYK-340 (manufactured by BYK-Chemie Japan), etc. As the silicone-based surfactant, it is preferable to use a polyester-modified silicone or a polyether-modified silicone. Specific examples include BYK-313, 315N, 322, 326, 331, 347, 348, BYK-UV3500, 3510, 3530, 3570 (all manufactured by BYK-Chemie Japan), etc. As the acetylene glycol-based surfactant, specific examples include Surfynol (registered trademark) 82, 104, 465, 485, TG (all manufactured by Air Products Japan), Olfin (registered trademark) STG, E1010 (all manufactured by Nisshin Chemical Co., Ltd.), etc.

[0093] The surfactant is not limited to the above, and any anionic, cationic, amphoteric or nonionic surfactant can be used, and it may be appropriately selected according to the addition purpose.

[0094] [Other components] The non-aqueous ink composition according to this embodiment may contain known additives such as stabilizers such as antioxidants and ultraviolet absorbers, polyvalent carboxylic acids such as epoxidized products, surface modifiers, slip agents, leveling agents (acrylic-based, silicone-based, etc.), defoamers, pH adjusters, bactericides, preservatives, deodorants, charge adjusters, wetting agents, etc. as optional components. Specific examples of the antioxidant include, for example, hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, hydrazine-based antioxidants, etc. Specifically, BHA (2,3-butyl-4-methoxyanisole), BHT (2,6-di-t-butyl-p-cresol), etc. are exemplified. Further, as the ultraviolet absorber, a benzophenone-based compound or a benzotriazole-based compound can be used. Specific examples of the epoxidized product include epoxidized glyceride, epoxidized fatty acid monoester, and epoxy hexahydrophthalate, etc., and specifically, Adeka Sizer O-130P, Adeka Sizer O-180A (manufactured by ADEKA Corporation), etc. are exemplified. Specific examples of the polyvalent carboxylic acid include citric acid, maleic acid, etc.

[0095] <2. Manufacturing method of ink composition> The manufacturing method of the ink composition according to this embodiment can be manufactured by mixing an alkylamide-based solvent (a), an organic solvent (b) having an evaporation enthalpy (EOV) of 45 kJ / mol or more, and each main component (for example, resin, coloring material, etc.) using a paint shaker. At this time, each component may be dispersed with zirconia beads. Further, the obtained non-aqueous ink composition may be adjusted to a desired dissolved oxygen amount or dissolved nitrogen amount by performing degassing treatment or the like as necessary.

[0096] Also, it is preferable to dry the organic solvent in advance. By drying the organic solvent in advance, the amount of moisture contained in the non-aqueous ink composition can be reduced. Examples of the method for drying the organic solvent include a method of blowing an inert gas (e.g., nitrogen gas) dried under an inert gas atmosphere such as nitrogen for a predetermined time, a method of distilling and purifying the organic solvent, a method of permeating the organic solvent through a semi-permeable membrane that selectively permeates water, and a method of selectively adsorbing the water mixed in the organic solvent by a water adsorbent that adsorbs water, etc.

[0097] <3. Recording method using the ink composition> The recording method according to this embodiment is a recording method of discharging the above non-aqueous ink composition onto the surface of a substrate by an inkjet method. The above non-aqueous ink composition is excellent in surface dryness and anti-blocking property of the recording material, and can obtain a recording material showing excellent glossiness. Also in the recording method according to this embodiment, a recording material excellent in surface dryness and anti-blocking property of the recording material and showing excellent glossiness can be obtained. The method of discharging by the inkjet method may be a piezo method using a piezoelectric element or a thermal method using a heating element, and is not particularly limited.

[0098] Then, it is preferable to heat the non-aqueous ink composition landed on the substrate (recording medium) by a heating mechanism provided in the inkjet recording apparatus. Thereby, by drying the non-aqueous ink composition landed on the substrate (recording medium), not only the alkylamide-based solvent (a) but also the organic solvent (b) having an evaporation enthalpy (EOV) of 45 kJ / mol or more can be dried, so that the surface dryness and anti-blocking property of the recording material can be further improved. The same applies to the method for manufacturing a recording material described later.

[0099] <4. Method for manufacturing a recording material> The recording method using the above ink composition can also be defined as a method for manufacturing a recording material. Also in the method for manufacturing a recording material according to this embodiment, a recording material excellent in surface dryness and anti-blocking property of the recording material and showing excellent glossiness can be obtained.

[0100] <5. Recorded matter> Each layer constituting the recorded matter manufactured by the method for manufacturing a recorded matter of the above-described embodiment will be described.

[0101] [Medium (recording medium)] The base material (recording medium) that can be used in the recording method according to the present embodiment is not particularly limited, and may be a non-absorbent base material such as a resin base material, a metal plate, or glass, or an absorbent base material such as paper or cloth, or a base material having a surface coating such as a base material provided with a receiving layer, and various base materials can be used.

[0102] Among these, since the non-aqueous ink composition is a non-aqueous ink composition that does not contain water, those mainly composed of resin on the surface are preferable. In particular, since the above non-aqueous ink composition contains an alkylamide-based solvent (a) that exhibits permeability to the resin base material, bleeding of printing on a medium (recording medium) having a resin surface is reduced and the printing becomes clear. Examples of the resin include polyvinyl chloride-based polymers, acrylics, PET, polycarbonate, PE, PP, and the like. Further, it may be used for a resin base material (so-called resin base material for lamination) on the premise that a film is laminated on the recording surface of the recorded matter. In particular, a base material (recording medium) having a surface made of a hard or soft polyvinyl chloride-based polymer is preferable. Examples of the base material (recording medium) having a surface made of a polyvinyl chloride polymer include a polyvinyl chloride base material (film or sheet).

[0103] [Recording layer] The recording layer is a layer formed by volatilization of the solvent contained in the above non-aqueous ink composition, and is a layer that forms a desired image. By discharging the above non-aqueous ink composition, a recorded matter excellent in surface dryness and blocking resistance and exhibiting excellent glossiness can be obtained.

[0104] In addition, the layer formed by the evaporation of the solvent contained in the above non-aqueous ink composition may be formed from a plurality of layers. For example, a layer of color ink (e.g., yellow, magenta, cyan, black) of the above non-aqueous ink composition may be formed on the layer of white ink of the above non-aqueous ink composition.

[0105] [Other layers] The recording medium according to this embodiment may further include a layer having a desired function on the upper surface of the decorative layer. For example, for the purpose of further imparting abrasion resistance and glossiness to the recording medium, an overcoat layer containing at least one of resin and wax may be formed. Also, a layer expressing an uneven texture (mat surface) may be formed by containing a filler or changing the film thickness in pixel units. Further, for imparting weather resistance to the recording medium, a weather-resistant layer containing an ultraviolet absorber or a light stabilizer, a luminous layer containing a luminous pigment, or the like may be formed.

[0106] In the recording medium according to this embodiment, a recording medium including a recording layer formed by the above non-aqueous ink composition has been described. However, for example, the above non-aqueous ink composition may be ejected onto a recording layer formed by a conventionally known ink composition to form a layer having a desired function. Also, the above non-aqueous ink composition may be ejected onto the recording layer formed by the above non-aqueous ink composition to form a layer having a desired function.

[0107] <6. Inkjet recording apparatus> An inkjet recording apparatus that ejects the above non-aqueous ink composition by an inkjet method can use a conventionally known one. For example, an inkjet printer such as VersaArt RE-640, manufactured by Roland DG Corporation, can be used.

[0108] As an example of the configuration of an inkjet recording apparatus, an on-carriage type serial printer type inkjet recording apparatus will be described. However, the inkjet recording apparatus capable of implementing the recording method according to the present embodiment may be an off-carriage type inkjet recording apparatus in which an ink cartridge is fixed externally, or may be a line printer type inkjet recording apparatus that discharges an ink composition onto a recording medium (base material) without moving the inkjet head.

[0109] Further, it is preferable that the inkjet recording apparatus includes a heating mechanism and a fixing mechanism for fixing the base material. By controlling the surface temperature of the base material by the heating mechanism provided in the inkjet recording apparatus and drying the non-aqueous ink composition landed on the base material (recording medium), it becomes possible to volatilize the organic solvent contained in the non-aqueous ink composition. In particular, since the above non-aqueous ink composition contains an organic solvent (b) having an evaporation enthalpy (EOV) of 45 kJ / mol or more that is relatively difficult to volatilize, this organic solvent (b) can be quickly volatilized by the heating mechanism.

[0110] Furthermore, the fixing mechanism for fixing the base material enables the non-aqueous ink composition to be dried while the base material (recording medium) is fixed, and can suppress the uneven heat application due to the deflection of the base material by heating. As a result, it becomes possible to effectively dry the non-aqueous ink composition landed on the base material (recording medium).

[0111] The heating mechanism provided in the inkjet recording apparatus may be a preheater, a platen heater, an afterheater, etc., or may be a mechanism for blowing warm air onto the recording object. Also, a plurality of these heating mechanisms may be combined.

[0112] The surface temperature of the substrate heated by the heating mechanism is not particularly limited as long as the organic solvent contained in the non-aqueous ink composition can be volatilized. 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.

[0113] The fixing mechanism for fixing the substrate may be a fixing mechanism that fixes the substrate with a predetermined jig or a fixing mechanism that sucks and adsorbs the substrate by negative pressure, and is not particularly limited.

[0114] The inkjet head that discharges the above non-aqueous ink composition may be a piezo-type inkjet head using a piezoelectric element or a thermal-type inkjet head using a heating element, and is not particularly limited.

[0115] Further, the inkjet recording apparatus may include a plastic tube that connects a container (such as an ink cartridge or a bottle) for storing the above non-aqueous ink composition and an inkjet head that discharges the above non-aqueous ink composition, and the above non-aqueous ink composition is supplied to the inkjet head through this plastic tube and is configured to be discharged by an inkjet method. When the non-aqueous ink composition is present in the plastic tube, a part of the organic solvent contained in the non-aqueous ink composition may volatilize. Then, the component amount of the organic solvent contained in the non-aqueous ink composition may change at the stage of inkjet discharge, and the desired characteristics may not be obtained.

[0116] In particular, the alkylamide-based solvent (a) contained in the above non-aqueous ink composition has a relatively low evaporation rate even when present in a plastic tube compared to other organic solvents. The evaporation rate of the organic solvent in the plastic tube is not necessarily correlated with the volatility parameters of the organic solvent itself, such as the boiling point, flash point, and evaporation enthalpy of the organic solvent. This is because the permeability of the organic solvent to the plastic varies depending on the type of the organic solvent, and the evaporation rate in a sealed low-density polyethylene tube is rather due to the permeability to the plastic. Specifically, it is a parameter caused by the chemical structure, molecular weight, compatibility, etc. of the organic solvent.

[0117] Since the alkylamide-based solvent is a solvent with a relatively low evaporation rate in the plastic tube, for a non-aqueous ink composition containing the alkylamide-based solvent, it is possible to perform inkjet ejection while maintaining the component amount of the organic solvent contained in the non-aqueous ink composition.

[0118] The evaporation rate of the organic solvent in the plastic tube can be determined by filling the organic solvent into a low-density polyethylene tube (a polyethylene tube hose manufactured by AS ONE Corporation (model number: 6-608-03, low-density polyethylene (PE-LD) with an inner diameter of 3 mm and an outer diameter of 5 mm), cutting it into 12 cm tubes), sealing them, storing them at 50 °C for one week, and measuring the evaporation rate after storage. For example, the evaporation rate of diethylene glycol dimethyl ether is 68% by mass, diethylene glycol methyl ethyl ether is 58% by mass, diethylene glycol diethyl ether is 54% by mass, dipropylene glycol dimethyl ether is 59% by mass, while N,N-diethylformamide is 11% by mass, N,N-diethylpropanamide is 12% by mass, and N,N-diethylacetamide is 13% by mass. It can be seen that the alkylamide-based solvent is a solvent with a low evaporation rate in the plastic tube.

[0119] The material of the plastic tube is not particularly limited, and examples thereof include polyolefin resins such as polyethylene resins, ethylene propylene diene rubber, nylon, polyurethane, PTFE, etc. Among these, polyethylene resins and ethylene propylene diene rubber are preferred.

[0120] In addition, the inkjet recording apparatus according to the present embodiment can also be used for inks of various colors such as yellow, magenta, cyan, black, etc., and also for light magenta, light cyan, light black, orange, green, red, white, etc. as described above. The order of the colors to be printed, the position and configuration of the head are not particularly limited. Further, the inkjet recording apparatus according to the present embodiment may or may not be provided with a winding mechanism for the recording medium (substrate), a drying mechanism for drying the surface of the substrate, and an ink circulation mechanism.

Examples

[0121] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these descriptions in any way.

[0122] 1. Preparation of resin (1) Acrylic resin A mixture of 150 g of methyl methacrylate, 50 g of butyl methacrylate and a predetermined amount of t-butyl peroxy-2-ethylhexanoate (polymerization initiator) was dropped into 300 g of diethylene glycol diethyl ether maintained at 100°C over 1.5 hours. After completion of the dropping, the reaction was carried out at 100°C for 2 hours and then cooled to obtain a colorless transparent polymer solution of methyl methacrylate. Thereafter, the solvent was sufficiently distilled off from this polymer solution to obtain a polymer of methyl methacrylate. At this time, the amount of t-butyl peroxy-2-ethylhexanoate as the polymerization initiator was changed to control the polymerization average molecular weight of methyl methacrylate (acrylic resin) to be 30,000 to 105,000 (the mass of the polymerization initiator used at this time is described in Table 1 below. It is denoted as "initiator amount" in Table 1).

[0123] (2) Vinyl chloride-vinyl acetate copolymer resin Into an autoclave equipped with a stirring device, after nitrogen substitution, 100 parts by mass of deionized water, 40 parts by mass of methanol, 32 parts by mass of vinyl chloride, 5 parts by mass of vinyl acetate, 0.2 parts by mass of glycidyl methacrylate, 3.55 parts by mass of hydroxypropyl acrylate, 0.1 parts by mass of hydroxypropyl methylcellulose (suspending agent), 0.026 parts by mass of di-2-ethylhexyl peroxydicarbonate (polymerization initiator), and a predetermined amount of di-3,5,5-trimethylhexanol peroxide (polymerization initiator) were charged. The temperature was raised to 63 °C while stirring under a nitrogen gas atmosphere. Immediately after reaching 63 °C, 48 parts by mass of vinyl chloride was continuously pressure-fed over 6 hours, and a mixture of 0.6 parts by mass of glycidyl methacrylate and 10.65 parts of hydroxypropyl acrylate was continuously pressure-fed over 5.4 hours for copolymerization reaction. When the internal pressure in the autoclave reached 0.3 MPa, the residual pressure was released, cooled, and the resin slurry was taken out, filtered, and dried to obtain a vinyl chloride-based copolymer resin. At this time, the amount of di-3,5,5-trimethylhexanol peroxide as the polymerization initiator was changed to control the polymerization average molecular weight of the vinyl chloride-vinyl acetate copolymer resin to be 40,000 to 75,000 (the mass of the polymerization initiator used at this time is described in Table 1 below. It is denoted as "initiator amount" in Table 1).

[0124] (3) Cellulose-based resin Commercially available cellulose-based resins (CAB551-0.01 and CAB553-0.4 from EASTMAN CHEMICAL) were used.

[0125] Table 1 shows the weight-average molecular weight (relative molecular mass) of each resin (acrylic resin, vinyl chloride-vinyl acetate copolymer resin, cellulose resin), and the proportion of resins having an intrinsic viscosity of 90 mL / g or more at 25°C. The weight-average molecular weight (relative molecular mass) was measured by GPC (gel permeation chromatography). The proportion of resins having an intrinsic viscosity of 90 mL / g or more was determined by connecting a viscosity detector (ViscoStarIII manufactured by Wyatt Corporation) and a refractive index detector (Optilab T-rEX manufactured by Wyatt Corporation) to a Shimadzu SEC (GPC) system, using tetrahydrofuran as the eluent, first passing the sample through a column heated to 40°C in the Shimadzu SEC (GPC) system, and then cooling the eluate to 25°C and measuring the specific viscosity SP 〔η SP 〕 with the viscosity detector and the concentration C with the refractive index detector, and extrapolating the concentration C to 0 in Lim(〔η

[0126]

Table 1

[0127] 2. Preparation of non-aqueous ink compositions Non-aqueous ink compositions of Examples and Comparative Examples were prepared such that each organic solvent, resin, dispersant, and pigment (colorant) had the proportions shown in the following table. Specifically, each component was dispersed with zirconia beads using a paint shaker to prepare the non-aqueous ink composition. The unit is mass%.

[0128] 3. Evaluation 1 (Glossiness) The glossiness of the non-aqueous ink compositions of the examples and comparative examples was evaluated. Specifically, the non-aqueous ink compositions of the examples and comparative examples were printed on a recording medium (adhesive polyvinyl chloride film (IMAGin JT5829R: manufactured by MACtac)) by an inkjet method using an inkjet printer (trade name VersaArt RE-640, manufactured by Roland DG Corporation) in a high-quality printing mode (1440x720 dpi) at a substrate surface temperature of 40°C for solid parts, and after drying in a 60°C oven for 5 minutes, the 20° glossiness of the printed matter was measured. The glossiness was measured with a handy-type gloss meter Phopoint IQ-S (manufactured by Konica Minolta) (in the table, denoted as "glossiness"). Evaluation criteria Evaluation 5: 20° gloss is 70 or more Evaluation 4: 20° gloss is 65 or more and less than 70 Evaluation 3: 20° gloss is 55 or more and less than 65 Evaluation 2: 20° gloss is 50 or more and less than 55 Evaluation 1: 20° gloss is less than 50

[0129] (Surface drying property) The surface drying property of the non-aqueous ink compositions of the examples and comparative examples was evaluated. Specifically, in the same manner as the above glossiness evaluation, a solid image was printed on a recording medium (adhesive polyvinyl chloride film (IMAGin JT5829R: manufactured by MACtac)) in a high-quality printing mode (1440x720 dpi), and the time until drying at 40°C was measured (in the table, denoted as "surface drying property"). Evaluation criteria Evaluation 5: Dries in less than 2 minutes. Evaluation 4: Dries in 2 minutes or more and less than 4 minutes. Evaluation 3: Dries in 4 minutes or more and less than 6 minutes. Evaluation 2: Dries in 6 minutes or more and less than 8 minutes. Evaluation 1: Dries in 8 minutes or more.

[0130] (Blocking resistance) The blocking resistance of the non-aqueous ink compositions of the examples and comparative examples was evaluated. Specifically, in the same manner as the above gloss evaluation, high-quality printing mode (1440x720 dpi) was used to print the solid portions on a recording medium (pressure-sensitive polyvinyl chloride film (IMAGin JT5829R: manufactured by MACtac)) at a substrate surface temperature of 40°C. After winding up the recording, it was left for 24 hours, then unfolded, and the ink transfer to the back surface overlapping the recording surface of the film and the recording surface were evaluated (in the table, denoted as "blocking resistance"). Evaluation criteria Evaluation 5: There is no ink transfer to the back surface after winding up, and there is no roughness on the recording surface. Evaluation 4: There is no ink transfer to the back surface after winding up, but there is slight roughness on the recording surface, and the design property is not impaired. Evaluation 3: Slight ink transfer to the back surface is observed after winding up, and slight traces are also seen on the recording surface. Evaluation 2: Clear ink transfer to the back surface is observed after winding up, and traces are seen on the recording surface. Evaluation 1: Marked ink transfer to the back surface is observed after winding up, and the design property of the recording surface is significantly impaired.

[0131] (Intermittent ejection property) The intermittent ejection property of the non-aqueous ink compositions of the examples and comparative examples was evaluated. Specifically, in the same manner as the above gloss evaluation, in a bidirectional high-speed printing mode (360x720 dpi) on a recording medium (pressure-sensitive polyvinyl chloride film (IMAGin JT5829R: manufactured by MACtac)) at a substrate surface temperature of 40°C over a long period at normal temperature, intermittent printing was performed on the above recording medium, and the presence or absence of dot omission, flight deviation, and ink splashing was observed, and the occurrence times were counted and evaluated (in the table, denoted as "intermittent ejection property"). Evaluation criteria Evaluation 5: Within the 24-hour test period, the occurrence of dot omission, flight deviation, or ink splashing was less than 10 times. Evaluation 4: Within the 24-hour test period, the occurrence of dot omission, flight deviation, or ink splashing was 10 times or more and less than 20 times. Evaluation 3: During the 24-hour test period, the occurrence of dot omission, flying curve, or ink splashing was more than 20 times and less than 30 times. Evaluation 2: During the 24-hour test period, the occurrence of dot omission, flying curve, or ink splashing was more than 30 times and less than 40 times. Evaluation 1: During the 24-hour test period, the occurrence of dot omission, flying curve, or ink splashing was 40 times or more.

[0132] (Solid filling) The solid filling of the non-aqueous ink compositions of the examples and comparative examples was evaluated. Specifically, in the same manner as the above gloss evaluation, printing was carried out on a recording medium (adhesive polyvinyl chloride film (IMAGin JT5829R: manufactured by MACtac)) in a bidirectional high-speed printing mode (360x720dpi) at a substrate surface temperature of 40°C, and the filling (white void) of the solid-printed part was confirmed (in the table, denoted as "solid filling"). Evaluation criteria Evaluation 5: A uniform solid has been formed. Evaluation 4: No white void can be visually confirmed, but slight color unevenness can be confirmed, and the design property is not impaired. Evaluation 3: No white void can be visually confirmed, but color unevenness can be confirmed. Evaluation 2: White void can be confirmed. Evaluation 1: Obvious white void can be confirmed, and a decrease in density perception is observed.

[0133] (Bleeding property) The bleeding property of the non-aqueous ink compositions of the examples and comparative examples was evaluated. Specifically, in the same manner as the above gloss evaluation, an image with 6pt characters of a color different from the solid part in the solid part of each color was printed on a recording medium (adhesive polyvinyl chloride film (IMAGin JT5829R: manufactured by MACtac)) in a high-quality printing mode (1440x720dpi) at a substrate surface temperature of 40°C. After drying the obtained printed matter in an oven at 60°C for 5 minutes, the bleeding of the printed matter was observed visually and with a loupe (x10) (in the table, denoted as "bleeding property"). Evaluation criteria Evaluation 5: No ink bleeding is observed by loupe observation. Evaluation 4: No bleeding of the ink was observed visually, and the 6-pt characters were clear. Evaluation 3: Slight bleeding of the ink was observed visually, but the designability was not impaired. Evaluation 2: Bleeding of the ink was observed visually, but the 6-pt characters were distinguishable. Evaluation 1: Significant bleeding of the ink was observed visually, and the 6-pt characters were not visible.

[0134] (Component Compatibility) The component compatibility (component compatibility of the inkjet head) of the non-aqueous ink compositions of the examples and comparative examples was evaluated. Specifically, 0.2 g of a cured product obtained by drying an epoxy adhesive (two-component curable epoxy adhesive "1500", manufactured by Semidain Co., Ltd.) used for the components of the inkjet head at 60°C for 1 day was immersed in the ink compositions of the examples and comparative examples, left at 60°C for 1 week, and an immersion test was conducted to measure the weight change of the cured product (indicated as "component compatibility" in the table). Evaluation Criteria Evaluation 5: The weight change rate is less than 3%, and there is no deterioration of the epoxy adhesive material. Evaluation 4: The weight change rate is 3% or more and less than 5%, and there is no deterioration of the epoxy adhesive material. Evaluation 3: The weight change rate is 5% or more and less than 10%, and there is no deterioration of the epoxy adhesive material. Evaluation 2: The weight change rate is 10% or more and less than 15%, and there is no deterioration of the epoxy adhesive material. Evaluation 1: The weight change rate is 15% or more and / or there is deterioration of the epoxy adhesive material.

[0135] [Table 2]

[0136] [Table 3]

[0137] [Table 4]

[0138]

Table 5

[0139]

Table 6

[0140]

Table 7

[0141]

Table 8

[0142]

Table 9

[0143] In the table, 「BTG」 means triethylene glycol monobutyl ether.

[0144] In the table, 「BTeG」 means tetraethylene glycol monobutyl ether.

[0145] In the table, 「BHeG」 means hexaethylene glycol monobutyl ether.

[0146] In the table, 「MFTG」 means tripropylene glycol monomethyl ether.

[0147] In the table, 「MFDG」 means dipropylene glycol monomethyl ether.

[0148] In the table, 「DEGDBE」 means diethylene glycol dibutyl ether.

[0149] In the table, "DEGMBEA" refers to diethylene glycol monobutyl ether acetate.

[0150] In the table, "PC" refers to propylene carbonate.

[0151] In the table, "DESU" refers to diethyl succinate.

[0152] In the table, "EL" refers to ethyl lactate.

[0153] In the table, "3-MBOH" refers to 3-methoxybutanol.

[0154] In the table, "MOZ" refers to 3-methyl-2-oxazolidinone.

[0155] In the table, "CATE" refers to triethyl citrate.

[0156] In the table, "ECL" refers to ε-caprolactone.

[0157] In the table, "DEF" refers to N,N-diethylformamide.

[0158] In the table, "DEPA" refers to N,N-diethylpropionamide.

[0159] In the table, "DEAA" refers to N,N-diethylacetamide.

[0160] In the table, "DMF" refers to N,N-dimethylformamide.

[0161] In the table, "MEDG" refers to diethylene glycol methyl ethyl ether.

[0162] In the table, "DEDG" refers to diethylene glycol diethyl ether.

[0163] In the table, "DMFDG" refers to dipropylene glycol dimethyl ether.

[0164] In the table, "PMA" refers to propylene glycol monomethyl ether acetate.

[0165] In the table, "GBL" refers to γ-butyrolactone.

[0166] In the table, "M100" refers to N,N-dimethyl-β-methoxypropionamide.

[0167] In the table, "ML" refers to methyl lactate.

[0168] In the table, "Solsperse32000" is a polycaprolactone-based dispersant manufactured by Lubrizol Corporation.

[0169] In the table, "Solsperse33000" is a polycaprolactone-based dispersant manufactured by Lubrizol Corporation.

[0170] As can be seen from Tables 2 to 9, it can be understood that for a non-aqueous ink composition of an example containing an alkylamide-based solvent (a) and an organic solvent (b) having an evaporation enthalpy (EOV) of 45 kJ / mol or more, a recording material excellent in surface dryness and blocking resistance and showing excellent glossiness can be obtained.

[0171] Particularly, in the non-aqueous ink compositions of Examples 1 to 8 in which the content of the organic solvent (b) having an evaporation enthalpy (EOV) of 45 kJ / mol or more was changed, Examples 3 to 8 in which the content of the organic solvent (b) was 5% by mass or more in the total amount of the non-aqueous ink composition were particularly excellent in glossiness. Furthermore, Examples 1 to 5 in which the content of the organic solvent (b) was 15% by mass or less in the total amount of the non-aqueous ink composition were able to obtain a recording material with even better surface dryness and less bleeding of the printing.

[0172] Also, in the non-aqueous ink compositions of Examples 9 to 17 in which the content of the alkylamide-based solvent (a) was changed, in Examples 11 to 17 where the content of the alkylamide-based solvent (a) was 5% by mass or more in the total amount of the non-aqueous ink composition, recording materials with excellent surface drying properties could be obtained. And in Examples 12 to 17 where the content of the alkylamide-based solvent (a) was 10% by mass or more in the total amount of the non-aqueous ink composition, bleeding of the printing was further reduced. Furthermore, in Examples 9 to 13 where the content of the alkylamide-based solvent (a) was 45% by mass or less in the total amount of the non-aqueous ink composition, the glossiness was good.

[0173] Also, in the non-aqueous ink compositions of Examples 18 to 30 in which the type of the organic solvent (b) with an evaporation enthalpy (EOV) of 45 kJ / mol or more was changed, the surface drying property and the glossiness were well balanced.

[0174] Also, in the non-aqueous ink compositions of Examples 42 to 58 in which the content of the resin with an intrinsic viscosity at 25°C of 90 mL / g or more was changed, the non-aqueous ink compositions of the examples where the resin with an intrinsic viscosity at 25°C of 90 mL / g or more was in the range of 5% by mass or less in the total amount of the resin had improved solid filling and intermittent ejection properties compared to the non-aqueous ink compositions of the examples in the range of more than 5% by mass.

[0175] On the other hand, in Comparative Examples 1 to 3 that did not contain an organic solvent (b) with an evaporation enthalpy (EOV) of 45 kJ / mol or more, the glossiness of the resulting recording was reduced, and furthermore, the intermittent ejection property was also deteriorated. In particular, in Comparative Example 3 containing γ-butyrolactone (a lactone-based solvent), the glossiness of the recording surface of the resulting recording was particularly deteriorated. Further, in Comparative Example 4 that did not contain an alkylamide-based solvent (a) and did not contain an organic solvent that penetrates into the resin base material, the surface drying property of the resulting recording was reduced, and furthermore, bleeding occurred. In addition, in Comparative Example 5 containing γ-butyrolactone (a lactone-based solvent) and an organic solvent (b) with an evaporation enthalpy (EOV) of 45 kJ / mol or more, back transfer (blocking resistance) to the back surface overlapping the recording surface of the recording occurred. Furthermore, in Comparative Example 6 containing N,N-dimethyl-β-methoxypropionamide, the member compatibility was deteriorated.

[0176] 4. Evaluation 2 The non-aqueous ink composition of Example 4 above was ejected by an inkjet method, and "bleeding property" and "solid filling" were evaluated in the same manner as above. At this time, the on / off of the heating mechanism and the fixing mechanism for fixing the base material provided in the inkjet recording apparatus was switched as shown in Table 10 below.

[0177] [Table 10]

[0178] As can be seen from Table 10, by using an inkjet recording apparatus equipped with a heating mechanism and a fixing mechanism for fixing the base material, turning on each mechanism, and drying the non-aqueous ink composition in a state where the base material (recording medium) is fixed by the fixing mechanism for fixing the base material, and ejecting the non-aqueous ink composition containing an alkylamide-based solvent (a) and an organic solvent (b) with an evaporation enthalpy (EOV) of 45 kJ / mol or more by an inkjet method, it can be seen that the "bleeding property" and "solid filling" of the resulting recording are good.

Claims

1. A non-aqueous ink composition containing an organic solvent and ejected by an inkjet method, wherein the organic solvent comprises an alkylamide-based solvent (a) and an organic solvent (b) having an evaporation enthalpy (EOV) of 45 kJ / mol or more and different from the alkylamide-based solvent (a), and contains the alkylamide-based solvent (a) contains an amide-based solvent represented by the following formula (2), a non-aqueous ink composition. 【Chemical 1】 (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 organic solvent (b) contains at least one selected from the group consisting of glycol ether dialkyl, glycol ether monoalkyl, acetate, cyclic ester, carbonate ester, dibasic acid ester, lactate ester, amide, and alcohol The non-aqueous ink composition according to claim 1.

3. The content of the organic solvent (b) is in the range of 1% by mass or more and 30% by mass or less in the total amount of the non-aqueous ink composition, The non-aqueous ink composition according to claim 1 or 2.

4. The alkylamide-based solvent (a) contains at least one selected from the group consisting of N,N-diethylformamide, N,N-diethylpropanamide, and N,N-diethylacetamide, The non-aqueous ink composition according to any one of claims 1 to 3.

5. The content of the alkylamide-based solvent (a) is in the range of 1% by mass or more and 90% by mass or less in the total amount of the non-aqueous ink composition, The non-aqueous ink composition according to any one of claims 1 to 4.

6. Further contains a resin, The resin has a specific viscosity at 25°C of 90 mL / g or more and is in the range of 5% by mass or less in the total amount of the resin The non-aqueous ink composition according to any one of claims 1 to 5.

7. Ejected by an inkjet method using an inkjet recording apparatus comprising a heating mechanism and a fixing mechanism for fixing a substrate The non-aqueous ink composition according to any one of claims 1 to 6.

8. Ejected by an inkjet method through a plastic tube using an inkjet recording apparatus equipped with the plastic tube The non-aqueous ink composition according to any one of claims 1 to 7.

9. The non-aqueous ink composition according to any one of claims 1 to 8 is ejected onto the surface of a substrate by an inkjet method Recording method.

10. The non-aqueous ink composition according to any one of claims 1 to 8 is ejected onto the surface of a substrate by an inkjet method Method for manufacturing a recorded matter.

11. A recorded matter in which a recording layer of the non-aqueous ink composition according to any one of claims 1 to 8 is formed on the surface of a substrate Recorded matter.

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