JP7169485B1 - Non-aqueous ink composition, ink set, recording method using the same, method for producing recorded matter, recorded matter, and inkjet recording apparatus - Google Patents

Abstract

A non-aqueous ink composition containing a perinone pigment can be suitably used as a non-aqueous ink composition ejected by an inkjet method. A non-aqueous ink composition ejected by an inkjet method containing a pigment, a pigment dispersant, an organic solvent, and a resin, wherein the pigment is represented by the following formula (1): A non-aqueous ink composition containing A, wherein the content of the pigment dispersant is smaller than the content of the pigment. (In formula (1), X1 to X12 are independently hydrogen, halogen atoms, alkyl groups, aromatic hydrocarbon groups, cyano groups, nitro groups, amino groups, -OH, -COOH, -COO-M+, - Indicates SO3H, -SO3-M+, etc., where M+ indicates a cation.) TIFF0007169485000011.tif42134 [Selection] None

Description

The present invention relates to a non-aqueous ink composition, an ink set, a recording method using the same, a method for producing a recorded matter, a recorded matter, and an inkjet recording apparatus.

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

For example, Patent Document 1 describes an aqueous pigment containing a perinone pigment and an azo compound as pigments, and an aqueous ink composition for inkjet recording using the same. Patent Literature 1 describes that this water-based ink composition contains a perinone-based pigment and an azo compound, thereby having good storage stability.

JP 2012-172070 A

Since perinone pigments have weather resistance, ink compositions containing perinone pigments are particularly suitable for producing recorded matter for outdoor use.

However, non-aqueous ink compositions containing perinone-based pigments tend to have poor ejection properties and storage stability, and the glossiness of the printed surface of the resulting printed matter and coating film resistance are reduced. It has become clear from the research of the present inventors that the characteristics required as a non-aqueous ink composition may not be satisfied.

An object of the present invention is to provide a non-aqueous ink composition containing a perinone pigment that can be suitably used as a non-aqueous ink composition ejected by an inkjet method. .

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by adjusting the content of the pigment and the pigment dispersant to a predetermined range, and have completed the present invention. rice field. Specifically, the present invention provides the following.

（式（１）中、Ｘ１～Ｘ１２はそれぞれ独立して、水素、ハロゲン原子、炭素数１以上５以下の分岐してもよいアルキル基、水素原子が置換されていてもよい芳香族炭化水素基、シアノ基、ニトロ基、アミノ基、－ＯＨ、－ＣＯＯＨ、－ＣＯＯ－Ｍ^＋、－ＳＯ_３Ｈ、－ＳＯ_３ ^－Ｍ^＋、水素原子が置換されていてもよいフタルイミド基、フタルイミドメチル基、又は複素環化合物を示し、Ｍ^＋はカチオンを示す。） (1) A non-aqueous ink composition ejected by an inkjet method containing a pigment, a pigment dispersant, an organic solvent, and a resin,
The pigment contains a pigment A represented by the following formula (1),
The content of the pigment dispersant is less than the content of the pigment,
Non-aqueous ink composition.

(In the formula (1), each of X1 to X12 is independently a hydrogen atom, a halogen atom, an optionally branched alkyl group having 1 to 5 carbon atoms, or an aromatic hydrocarbon group optionally substituted with a hydrogen atom. , a cyano group, a nitro group, an amino group, -OH, -COOH, -COO-M ⁺ , -SO ₃ H, -SO ₃ ^- M ⁺ , a phthalimido group optionally substituted with a hydrogen atom, a phthalimidomethyl group, or a heterocyclic compound, and M ⁺ indicates a cation.)

(2) the content of the resin is greater than the content of the pigment;
The non-aqueous ink composition according to (1).

(3) The content of the pigment is 1.0% by mass or more,
The non-aqueous ink composition according to (1) or (2).

(4) the content of the resin is greater than the content of the pigment dispersant;
The non-aqueous ink composition according to any one of (1) to (3).

(5) ((content of the pigment dispersant)/(content of the resin)) is less than 0.8;
The non-aqueous ink composition according to any one of (1) to (4).

(6) the content of the resin is greater than the total content of the pigment and the pigment dispersant;
The non-aqueous ink composition according to any one of (1) to (5).

(7) the content of the resin is greater than the total content of the pigment, the pigment dispersant, and the surfactant;
The non-aqueous ink composition according to any one of (1) to (6).

(8) ((Total content of the pigment dispersant and the surfactant)/(Content of the resin)) is 0.3 or more and less than 1.0.
The non-aqueous ink composition according to any one of (1) to (7).

(9) The content of the pigment A is
0.1% by mass or more and 8.0% by mass or less in the total amount of the non-aqueous ink composition,
The non-aqueous ink composition according to any one of (1) to (8).

(10) The content of water in the ink composition is 0.5% by mass or less.
The non-aqueous ink composition according to any one of (1) to (9).

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

(12) A method for producing recorded matter, comprising ejecting the non-aqueous ink composition according to any one of (1) to (10) onto the surface of a substrate by an inkjet method.

(13) An ink set comprising at least the non-aqueous ink composition according to any one of (1) to (10).

(14) A recorded matter in which a printed layer of the non-aqueous ink composition according to any one of (1) to (10) is formed on the surface of a substrate.

(15) An inkjet recording apparatus equipped with a container filled with the non-aqueous ink composition according to any one of (1) to (10).

The non-aqueous ink composition of the present invention satisfies the properties required as a non-aqueous ink composition ejected by an inkjet method even when a pigment containing a penoline pigment is used as the pigment.

Hereinafter, specific embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments at all, and can be implemented with appropriate modifications within the scope of the purpose of the present invention. can do.

≪1. Non-aqueous ink composition>>
The non-aqueous ink composition according to the present embodiment is a non-aqueous ink composition ejected by an inkjet method containing a pigment, a pigment dispersant, an organic solvent, and a resin. Here, the “non-aqueous ink composition” means an ink composition containing an organic solvent produced without intentionally containing water, unlike an aqueous ink composition containing water as a main component. means.

The pigment contained in this non-aqueous ink composition contains a pigment A represented by the following formula (1), and the content of the pigment dispersant contained in the non-aqueous ink composition is It is characterized by being smaller than the content of the pigment contained.

（式（１）中、Ｘ１～Ｘ１２は水素を含む置換基である。Ｘ１～Ｘ１２はそれぞれ独立して、水素、ハロゲン原子、炭素数１以上５以下の分岐してもよいアルキル基、水素原子が置換されていてもよい芳香族炭化水素基、シアノ基、ニトロ基、アミノ基、－ＯＨ、－ＣＯＯＨ、－ＣＯＯ^－Ｍ^＋、－ＳＯ_３Ｈ、－ＳＯ_３ ^－Ｍ^＋、水素原子が置換されていてもよいフタルイミド基、フタルイミドメチル基、又は複素環化合物を示し、Ｍ^＋はカチオンを示す。）

(In the formula (1), X1 to X12 are substituents containing hydrogen. X1 to X12 are each independently hydrogen, a halogen atom, an optionally branched alkyl group having 1 to 5 carbon atoms, a hydrogen atom optionally substituted aromatic hydrocarbon group, cyano group, nitro group, amino group, -OH, -COOH, -COO ^- M ⁺ , -SO ₃ H, -SO ₃ ^- M ⁺ , hydrogen atom substituted represents a phthalimido group, a phthalimidomethyl group, or a heterocyclic compound which may be substituted, and M ⁺ represents a cation.)

And the content of the pigment dispersant is smaller than the content of the pigment (less than the content of the pigment), so that the glossiness of the printed surface and the coating film resistance of the resulting printed matter are improved by the inkjet method. It is possible to satisfy the characteristics required as a non-aqueous ink composition to be ejected.

The water content in the non-aqueous ink composition according to the present embodiment is preferably 0.5% by mass or less, more preferably 0.3% by mass or less, based on the total amount of the non-aqueous ink composition. More preferably, it is 0.1% by mass. Since Pigment A is highly hydrophobic, a non-aqueous ink jet composition containing this pigment tends to deteriorate dispersibility of the pigment relatively easily due to contact with water, and storage stability tends to deteriorate. By reducing the water content in the non-aqueous ink composition so that it contains as little water as possible (intentionally avoiding water), storage stability, recovery from cleaning, etc. are improved. becomes possible.

Next, each component contained in the non-aqueous ink composition according to this embodiment will be described.

[Pigment]
The non-aqueous ink composition according to this embodiment contains a pigment. This pigment is characterized by containing a pigment A represented by the following formula (1).

（式（１）中、Ｘ１～Ｘ１２はそれぞれ独立して、水素、ハロゲン原子、炭素数１以上５以下の分岐してもよいアルキル基、水素原子が置換されていてもよい芳香族炭化水素基、シアノ基、ニトロ基、アミノ基、－ＯＨ、－ＣＯＯＨ、－ＣＯＯ－Ｍ^＋、－ＳＯ_３Ｈ、－ＳＯ_３ ^－Ｍ^＋、水素原子が置換されていてもよいフタルイミド基、フタルイミドメチル基、又は複素環化合物を示し、Ｍ^＋はカチオンを示す。）

(In the formula (1), each of X1 to X12 is independently a hydrogen atom, a halogen atom, an optionally branched alkyl group having 1 to 5 carbon atoms, or an aromatic hydrocarbon group optionally substituted with a hydrogen atom. , a cyano group, a nitro group, an amino group, -OH, -COOH, -COO-M ⁺ , -SO ₃ H, -SO ₃ ^- M ⁺ , a phthalimido group optionally substituted with a hydrogen atom, a phthalimidomethyl group, or a heterocyclic compound, and M ⁺ indicates a cation.)

Since such a pigment A has weather resistance, it is possible to improve the weather resistance of a printed material obtained from a non-aqueous ink composition containing the pigment A. Moreover, since the content of the pigment dispersant is smaller than the content of the pigment, it is possible to satisfy the characteristics required as a non-aqueous ink composition ejected by an inkjet method.

Substituents (X1 to X12) in the benzene ring in the molecular structure of Pigment A may be changed as appropriate. A method for changing the type of substituents (X1 to X12) includes a method of dispersing a pigment in an organic solvent and introducing a desired substituent with an additive capable of introducing a specific substituent. For example, it can be prepared by the method described in Patent No. 2993392, and when changing the type of substituents (X1 to X12) in the benzene ring, any of the 12 substitution positions on the benzene ring may be particularly There is no particular limitation, and the number of substituents is not particularly limited.

The average particle size of Pigment A is not particularly limited, but the upper limit of the volume-based cumulative 90% particle size D90 is preferably 500 nm or less, preferably 450 nm or less, and more preferably 400 nm. As a result, the storage stability is improved, the ink-jetting properties are improved, and the non-aqueous ink composition can be suitably used for ink-jetting. The lower limit of the volume-based cumulative 90% particle diameter D90 is preferably 50 nm or more, more preferably 100 nm or more. When the volume-based cumulative 90% particle diameter D90 of Pigment A is in such a range, the storage stability of the non-aqueous ink composition can be improved.

In this specification, "volume-based cumulative 90% particle diameter D90" means a particle diameter at which the cumulative volume calculated from the small diameter side becomes 90%. The measurement of the "volume-based cumulative 90% particle diameter D90" is exemplified by a particle size distribution measuring device (Microtrack Bell Co., Ltd. particle size analyzer NANOTRACWAVE, Otsuka Electronics Co., Ltd. particle size measuring device FPAR-1000, etc. ) can be used.

The content of pigment A is not particularly limited, but the lower limit of the content of pigment A is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, based on the total amount of the non-aqueous ink composition. It is more preferably 0.5% by mass or more, more preferably 1.0% by mass or more, particularly preferably 2.0% by mass or more, and 3.0% by mass or more. is most preferred. When the content of the pigment A is 0.1% by mass or more in the total amount of the non-aqueous ink composition, it is possible to improve the printing density, and the recording obtained by combining with the non-aqueous ink composition of other colors The color gamut of objects can be increased. The upper limit of the content of pigment A is preferably 8.0% by mass or less, more preferably 6.0% by mass or less, and even more preferably 5.0% by mass or less. When the content of pigment A is 8.0% by mass or less in the total amount of the non-aqueous ink composition, it becomes possible to relatively increase the content of other additives, and the dispersion stability of pigment A is improved. Furthermore, since the increase in the viscosity due to the increase in the content of the pigment A can be suppressed, clogging of the nozzles of the inkjet head can be suppressed.

As the pigment A represented by formula (1), C.I. I. Pigment Orange 43 may be mentioned. Pigment A of formula (1) may be synthesized, for example the commercially available C.I. I. Pigment Orange 43 is washed with a solution (acid solution, alkaline solution, or neutral solution) to treat the surface of the pigment or remove the substituents (X1~ It may be obtained by changing the type of X12), or by performing both processes. Commercially available products include A-76 manufactured by Arimoto Chemical Co., Ltd., Hostaperm Orange GR and PV Gast Orange GRL manufactured by Clariant, Fasogen Super Orange 6200 manufactured by DIC, and Lionogen Orange GR-F manufactured by Toyo Ink. be done.

Moreover, the non-aqueous ink composition according to the present embodiment may further contain coloring materials (including pigments and dyes) other than the pigment A described above. Examples of such colorants include pigments and dyes of hues similar to Pigment A (eg, orange, magenta, yellow, red). In this case, the content of all pigments including pigment A is preferably 1.0% by mass or more, particularly preferably 2.0% by mass or more, and most preferably 3.0% by mass or more. .

Examples of organic pigments other than Pigment A described above by color index (C.I.) number include C.I. I. Pigment Yellow 1, 2, 3, 12, 13, 14, 16, 17, 20, 24, 73, 74, 75, 83, 93, 95, 97, 98, 109, 110, 114, 117, 120, 125, 128, 129, 130, 137, 138, 139, 147, 148, 150, 151, 153, 154, 155, 166, 168, 180, 185, 213, 214, C.I. I. 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. I. Pigment Orange 16, 36, 43, 51, 55, 59, 61, 64, 71, 73, C.I. I. pigment violet 19, 23, 29, 30, 37, 40, 50, C.I. I. Pigment Brown 23, 25, 26 and the like.

In the total amount of pigment contained in the non-aqueous ink composition, the content of the pigment A is preferably 50% by mass or more, more preferably 70% by mass or more, and 90% by mass or more. More preferred.

[Pigment Dispersant]
The non-aqueous ink composition according to this embodiment contains a pigment dispersant. The content of the pigment dispersant is characterized by being smaller than the content of the pigment contained in the non-aqueous ink composition. As a result, it is possible to suppress the aggregation of the perinone pigment contained in the non-aqueous ink composition, and the glossiness of the printed surface of the resulting printed matter is improved. It becomes possible to satisfy the required characteristics.

The content of the pigment dispersant is preferably 5.0% by mass or less, more preferably 3.0% by mass or less, and preferably 2.0% by mass or less in the total amount of the non-aqueous ink composition. More preferred. The content of the pigment dispersant is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and more preferably 0.3% by mass or more in the total amount of the non-aqueous ink composition. It is more preferably 0.5% by mass or more, particularly preferably 0.5% by mass or more, and most preferably 1.0% by mass or more.

Any dispersant used in non-aqueous ink compositions can be used as the pigment dispersant. A polymer dispersant is preferably used as the pigment dispersant. As a polymer dispersant, the main chain consists of a polyester, polyacrylic, polyurethane, polyamine, polycaprolactone, etc., and has a polar group such as an amino group, a carboxyl group, a sulfone group, or a hydroxyl group as a side chain. It is. Among these, by using a polymer dispersant containing a polycaprolactone-based polymer dispersant, it is possible to more effectively suppress aggregation of the perinone pigment contained in the non-aqueous ink composition. .

For polyacrylic dispersants, for example, Disperbyk-2000, 2001, 2008, 2009, 2010, 2020, 2020N, 2022, 2025, 2050, 2070, 2095, 2150, 2151, 2155, 2163, 2164, BYKJET-9130, 9131 , 9132, 9133, 9151 (manufactured by Vic Chemie), Efka PX4310, PX4320, PX4330, PA4401, 4402, PA4403, 4570, 7411, 7477, PX4700, PX4701 (manufactured by BASF), TREPLUS D-1200, D-1410, D-1420, MD-1000 (manufactured by Otsuka Chemical Co., Ltd.), Floren DOPA-15BHFS, 17HF, 22, G-700, 900, NC-500, GW-1500 (manufactured by Kyoeisha Chemical Co., Ltd.), and the like are used. Polycaprolactone-based dispersants include, for example, Ajisper PB821, PB822, PB881 (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Hinoact KF-1000, T-6000, T-7000, T-8000, T-8000E, T-9050 ( Kawaken Fine Chemicals Co., Ltd.), Solsperse 20000, 24000, 32000, 32500, 32550, 32600, 33000, 33500, 34000, 35200, 36000, 37500, 39000, 71000, 76400, 76500, 86000, 88000, J10 TEGO Dispers 652, 655, 685, 688, 690 (manufactured by Evonik Japan) and the like are used.好ましい分散剤としては、ＢＹＫＪＥＴ－９１３０、９１３１，９１３２，９１３３，９１５１、ＥｆｋａＰＸ４３１０、ＰＸ４３２０、ＰＸ４３３０、ＰＸ４７００、ＰＸ４７０１、Ｓｏｌｓｐｅｒｓｅ２００００、２４０００、３２０００、３３０００、３３５００、３４０００、３５２００、３９０００、７１０００、７６５００、８６０００、 88000, J180, J200, TEGO Dispers 655, 685, 688, 690, etc. are used. These individual or mixtures thereof can be used.

In particular, when the substituents (X1 to X12) in the benzene ring in the molecular structure of Pigment A are introduced with substituents that exhibit acidic to weakly basic properties, a pigment dispersant having a basic group among the above is preferably used. Aggregation of the pigment A in the non-aqueous ink composition can be suppressed by using a pigment dispersant having a basic group.

Among these, it is preferable to use a pigment dispersant having an amine value in the range of 20 mgKOH/g or more and 100 mgKOH/g or less. Aggregation of Pigment A in the non-aqueous ink composition can be more effectively suppressed. Particularly when the pH of the pigment A is 8 or less (preferably 7 or less), the pigment dispersant having an amine value within a predetermined range is more likely to adhere to the surface of the pigment A. It becomes possible to effectively suppress aggregation of the pigment A in the composition.

The weight average molecular weight of these pigment dispersants is preferably 1,000 or more, more preferably 3,000 or more, and even more preferably 5,000 or more. The high-molecular-weight pigment dispersant can effectively suppress the aggregation of the pigment A, and can effectively suppress the aggregation of the pigment A in the non-aqueous ink composition. It is possible to make the storage stability of the good. Furthermore, it is possible to improve the coating film resistance of the printed matter.

[Dispersing aid]
A dispersing aid may be used as necessary in the non-aqueous ink composition according to the present embodiment. The dispersing aid is adsorbed on the surface of the coloring material (pigment), and the functional group increases the affinity with the organic solvent and dispersant in the non-aqueous ink composition, thereby improving the dispersion stability. As the dispersing aid, the pigment derivatives described above are preferable, and known pigment derivatives having functional groups such as acidic groups, basic groups, and neutral groups in the organic pigment residue can be used.

[resin]
The non-aqueous ink composition according to this embodiment contains a resin. In addition to the content of the pigment dispersant being less than the content of the pigment, by containing the resin, it is possible to suppress aggregation of the perinone pigment contained in the non-aqueous ink composition, and the obtained printed matter It is possible to satisfy the characteristics required as a non-aqueous ink composition ejected by an inkjet method, such as improved abrasion resistance of the printed surface. Furthermore, by containing a resin, the fixability, water resistance and stretchability of the recording layer formed from the non-aqueous ink composition can be improved.

Examples of resins include, but are not limited to, acrylic resins, polystyrene resins, polyester resins, vinyl chloride resins, vinyl acetate resins, vinyl chloride vinyl acetate copolymer resins, polyethylene resins, polyurethane resins, and rosin. Modified resin, phenol resin, terpene resin, polyamide resin, vinyl toluene-α-methylstyrene copolymer, ethylene-vinyl acetate copolymer, cellulose acetate butyrate, cellulose acetate propionate, silicone (silicon) based resins, acrylamide based resins, epoxy based resins, or copolymer resins or mixtures thereof can be used. Among these, those containing acrylic resins, vinyl chloride resins, cellulose resins, polyester resins, and polyurethane resins are preferable.

The acrylic resin is not particularly limited as long as it is contained as a main component of the monomer constituting the (meth)acrylic acid ester monomer. The acrylic resin may be a homopolymer of one kind of radically polymerizable monomer, or may be a copolymer of two or more kinds of selected radically polymerizable monomers. A preferred acrylic resin for the non-aqueous ink composition according to the embodiment is a polymer of methyl methacrylate, or selected from the group consisting of methyl methacrylate, butyl methacrylate, ethoxyethyl methacrylate, and benzyl methacrylate. It is a copolymer with at least one or more compounds that are Examples of commercially available (meth)acrylic resins include "Paraloid B99N", "Paraloid B60", "Paraloid B66" and "Paraloid B82" manufactured by Rohm and Haas.

The vinyl chloride resin may be either a homopolymer composed of a vinyl chloride monomer or a copolymer using two or more selected polymerizable monomers. Examples of copolymers of vinyl chloride resins include vinyl chloride-vinyl acetate copolymer resins. A vinyl chloride-vinyl acetate copolymer resin is a polymer of vinyl chloride monomer and vinyl acetate monomer. Vinyl chloride-vinyl acetate copolymer resins include, for example, vinyl chloride-vinyl acetate copolymer, vinyl chloride/vinyl acetate/maleic acid copolymer, vinyl chloride/vinyl acetate/vinyl alcohol copolymer, vinyl chloride/vinyl acetate / hydroxyalkyl acrylate copolymers, etc., and mixtures thereof. Examples of the vinyl chloride-vinyl acetate copolymer resin include "SOLBIN C, CL, CNL, CLL, CLL2, C5R, TA2, TA3, A, AL, TA5R, M5" from Nissin Chemical Industry Co., Ltd. It can be obtained and used under the trade name.

A vinyl chloride-vinyl acetate copolymer resin can be obtained by polymerizing a vinyl chloride monomer and a vinyl acetate monomer. A conventionally known polymerization method may be used as the polymerization method. The polymerization method is preferably emulsion polymerization or suspension polymerization, more preferably suspension polymerization.

A cellulose-based resin is a resin having a cellulose skeleton obtained by biologically or chemically introducing a functional group using cellulose as a raw material. For example, cellulose-based resins include cellulose acetate butyrate resins, cellulose acetate propionate resins, cellulose acetate alkylate resins such as cellulose acetate propionate butyrate resins, cellulose acetate resins, nitrocellulose resins, and mixtures thereof. mentioned. Examples of the cellulose resins include "CAB551-0.01", "CAB551-0.2", "CAB553-0.4", "CAB531-1", "CAB381-0.1" and "CAB381-0.1" available from EASTMAN. 5”, “CAB381-2”, “CAB381-20”, “CAP504”, “CAP482-0.5” and the like.

A polyester resin contains at least a structural unit obtained by polycondensation of an alcohol component and a carboxylic acid component. The polyester-based resin may include a modified polyester-based resin. Examples of polyester resins include "VYLON226", "VYLON270", "VYLON560", "VYLON600", "VYLON630", "VYLON660", "VYLON885", "VYLONGK250", "VYLONGK810", "VYLON GK890" manufactured by Toyobo Co., Ltd. It can be obtained and used under trade names such as "elitleUE-3200", "elitleUE-3285", "elitleUE-3320", "elitleUE-9800" and "elitleUE-9885" manufactured by Unitika.

A polyurethane resin contains at least a structural unit obtained by copolymerizing an alcohol component and an isocyanate component. Polyurethane-based resins may include polyurethane-based resins modified with polyester, polyether, or caprolactone. Examples of the polyurethane-based resins include "Uriano KL-424", "Uriano KL-564", "Uriano KL-593", and "Uriano 3262" available from Arakawa Chemical Industries, Ltd., and "Pandex 372E" and "Uriano 372E" available from DIC. Pandex 390E”, “Pandex 394E”, “Pandex 304”, “Pandex 305E”, “Pandex P-870”, “Pandex P-910”, “Pandex P-895”, “Pandex 4030", "Pandex 4110", and the like.

Further, these acrylic resins, vinyl chloride resins, cellulose resins, polyester resins, and polyurethane resins may be used alone, but it is preferable to use two of them in combination. It is more preferable to use a resin in which a resin and a vinyl chloride resin are mixed. The content ratio of the acrylic resin and the vinyl chloride resin can be controlled so as to meet the requirements for the non-aqueous ink composition, such as color development, drying properties, coating properties, and printability. When an acrylic resin and a vinyl chloride resin are mixed, the mixing ratio is not particularly limited and can be changed as appropriate.

These resins preferably have a weight average molecular weight of 10,000 or more, more preferably 15,000 or more, even more preferably 20,000 or more, and even more preferably 25,000 or more. It is possible to improve the abrasion resistance of the printed surface of the resulting printed matter. When the resin molecular weight is represented by the absolute molecular weight |Mw|, it is preferably 20,000 or more, more preferably 25,000 or more, and even more preferably 30,000 or more. The coating film resistance of the resulting printed material can satisfy the properties required as a non-aqueous ink composition ejected by an inkjet method.

The content of the resin in the non-aqueous ink composition according to the present embodiment is not particularly limited, but is preferably in the range of 0.05% by mass or more based on the total amount of the non-aqueous ink composition. It is more preferably contained in the range of 0.1% by mass or more, and further preferably in the range of 0.5% by mass or more. This can further improve the surface drying property of the obtained recorded matter. The resin contained in the non-aqueous ink composition is preferably contained in the range of 20.0% by mass or less, more preferably 15.0% by mass or less, based on the total amount of the non-aqueous ink composition. It is more preferable to contain in the range of 10.0% by mass or less. This makes it possible to more effectively eliminate clogging in the nozzles of the inkjet head and improve the storage stability of the non-aqueous ink composition.

The content of the pigment dispersant is preferably less than the content of the total pigment. Also, the content of the pigment dispersant is preferably smaller than the content of the pigment A. As a result, the glossiness of the printed surface of the resulting printed matter is further improved, and the color developability, abrasion resistance, and solvent resistance are excellent, and the characteristics required as a non-aqueous ink composition ejected by the inkjet method. is further satisfied. The ratio of the content of the pigment dispersant to the content of the total pigment or pigment A (pigment dispersant/total pigment, pigment dispersant/pigment A) in the non-aqueous ink composition is preferably less than 1.0. Less than 0.8 is more preferable, less than 0.7 is still more preferable, and less than 0.6 is particularly preferable. The lower limit is preferably 0.1 or more, more preferably 0.2 or more, and even more preferably 0.3 or more.

The resin content is preferably greater than the total pigment content. Moreover, it is preferable that the content of the resin is larger than the content of the pigment A. The ratio of the content of the pigment dispersant to the content of the total pigment or pigment A (pigment dispersant/total pigment, pigment dispersant/pigment A) in the non-aqueous ink composition is preferably less than 1.0. Less than 0.8 is more preferable, less than 0.7 is still more preferable, and less than 0.6 is particularly preferable. The lower limit is preferably 0.3 or more, more preferably 0.4 or more.

Also, the content of the resin is preferably greater than the content of the pigment dispersant contained in the non-aqueous ink composition. As a result, the glossiness of the printed surface of the resulting printed matter is further improved, and the color developability, abrasion resistance, and solvent resistance are excellent, and the characteristics required as a non-aqueous ink composition ejected by the inkjet method. is further satisfied.

Specifically, the ratio of the pigment dispersant content to the resin content (pigment dispersant/resin) in the non-aqueous ink composition is preferably less than 1.0, more preferably less than 0.8. , is more preferably less than 0.7, particularly preferably less than 0.6, and most preferably less than 0.4. The lower limit is preferably 0.1 or more, more preferably 0.15 or more, and even more preferably 0.2 or more.

In the present invention, the resin content is preferably larger than the total content of the pigment (or pigment A) and the pigment dispersant. As a result, the glossiness of the printed surface of the resulting printed matter is further improved, and the color developability, abrasion resistance, and solvent resistance are excellent, and the characteristics required as a non-aqueous ink composition ejected by the inkjet method. is further satisfied. The ratio of the total content of pigment (or pigment A) and pigment dispersant to the content of resin in the non-aqueous ink composition ((pigment (or pigment A) + pigment dispersant) / resin) is Less than 1.0 is preferred, less than 0.95 is more preferred, and less than 0.9 is even more preferred. The lower limit is preferably 0.1 or more, more preferably 0.5 or more, and even more preferably 0.6 or more.

In the present invention, the resin content is preferably larger than the total content of the pigment (or pigment A), pigment dispersant and surfactant. The ratio of the total content of pigment (or pigment A), pigment dispersant and surfactant to the content of resin in the non-aqueous ink composition, ((pigment (or pigment A) + pigment dispersant + Surfactant)/resin) is preferably less than 1.4, more preferably less than 1.2, and even more preferably less than 1.0. The lower limit is preferably 0.5 or more, more preferably 0.6 or more.

In the present invention, the resin content is preferably greater than the total content of the pigment dispersant and surfactant. The ratio of the total content of the pigment dispersant and the surfactant to the content of the resin in the non-aqueous ink composition, ((pigment dispersant + surfactant)/resin), is less than 1.0. Preferably, less than 0.8 is more preferable, and less than 0.6 is even more preferable. The lower limit is preferably 0.1 or more, more preferably 0.2 or more, and particularly preferably 0.3 or more.

In the present invention, the content of the pigment (or pigment A) is preferably greater than the total content of the pigment dispersant and surfactant. The ratio of the total content of the pigment dispersant and the surfactant to the content of the pigment (or pigment A) in the non-aqueous ink composition, ((pigment dispersant + surfactant) / pigment resin (or Pigment A)) is preferably less than 1.0, more preferably less than 0.8, even more preferably less than 0.6. The lower limit is preferably 0.1 or more, more preferably 0.2 or more, and even more preferably 0.3 or more.

[Organic solvent]
The non-aqueous ink composition according to this embodiment contains an organic solvent. The organic solvent is capable of dispersing or dissolving each component contained in the non-aqueous ink composition according to this embodiment. The organic solvent is not particularly limited, but organic solvent B (alkylamide solvent, cyclic amide solvent, and cyclic ester at least one selected from the group consisting of system solvents). Further, from the viewpoint of improving the ejection property of the non-aqueous ink composition and more effectively exhibiting the effects of the present invention, it is preferable to contain an organic solvent C (glycol ether dialkyl solvent).

The alkylamide-based solvent, cyclic amide-based solvent, and cyclic ester-based solvent contained in the organic solvent B will be described below.

[Organic solvent B]
(1) Alkylamide solvent An alkylamide solvent is a compound having an alkyl group (C _n H _2n+1 -) and a -C(=O)-N- group (amide bond). It is a solvent consisting of a compound composed of -C(=O)-N- groups. As the alkylamide-based solvent, those having, for example, the following structures can be preferably used.

（式（３）中、Ｒ_１は、水素若しくは炭素数１以上４以下のアルキル基であり、Ｒ_２、Ｒ_３は、それぞれ独立して水素若しくは炭素数１以上４以下のアルキル基を表す。

(In Formula (3), R ₁ is hydrogen or an alkyl group having 1 to 4 carbon atoms, and R ₂ and R ₃ each independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms.

R ₂ and R ₃ in formula (3) are preferably alkyl groups having 1 to 4 carbon atoms, and more preferably alkyl groups having 2 to 4 carbon atoms.

Specific examples of alkylamide solvents include N,N-diethylformamide, N,N-diethylacetamide, N,N-dipropylformamide, N,N-dibutylformamide, N,N-diethylpropanamide, N , N-dipropylpropanamide, N-ethylformamide, 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. preferable.

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

The upper limit of the alkylamide solvent content is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 75% by mass or less in the total amount of the non-aqueous ink composition.

(2) Cyclic Amide Solvent A cyclic amide solvent is a solvent having a cyclic structure and a —C(═O)—N— group in the cyclic structure. A cyclic amide solvent having, for example, the following structure can be preferably used.

（式（４）中、Ｒ_４は、炭素数３以上５以下のアルキレン基であり、Ｒ_５は、水素若しくは炭素数１以上２以下のアルキル基を表す。）

(In formula (4), R ₄ is an alkylene group having 3 to 5 carbon atoms, and R ₅ represents hydrogen or an alkyl group having 1 to 2 carbon atoms.)

Specific examples of cyclic amide solvents include N-methylcaprolactam, N-acetylcaprolactam, ε-caprolactam, N-vinylcaprolactam, 2-pyrrolidone, N-methyl-2-pyrrolidone, and N-ethyl-2-pyrrolidone. , N-propyl-2-pyrrolidone, N-ethyl-ε-caprolactam, N-propyl-ε-caprolactam, N-methyl-ε-caprolactam and the like. Among these, it is preferable to contain at least one selected from the group consisting of ε-caprolactam, N-methylcaprolactam, and N-vinylcaprolactam.

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

The upper limit of the content of the cyclic amide solvent is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 75% by mass or less in the total amount of the non-aqueous ink composition.

(3) Cyclic Ester-Based Solvent Examples of solvents having a cyclic ester structure include cyclic carbonate-based solvents and lactone-based solvents. As the lactone-based solvent, for example, one having the following structure can be preferably used.

（式（５）中、Ｒ_６は、炭素数３以上５以下のアルキレン基であり、Ｒ_７は、水素若しくは炭素数１以上２以下のアルキル基を表す。）なおＲ_６は、炭素数４以上５以下のアルキレン基がより好ましく、炭素数５のアルキレン基がより好ましい。

(In formula (5), R ₆ is an alkylene group having 3 to 5 carbon atoms, and R ₇ represents hydrogen or an alkyl group having 1 to 2 carbon atoms.) R ₆ has 4 carbon atoms. An alkylene group having 5 or less is more preferable, and an alkylene group having 5 carbon atoms is more preferable.

Lactone solvents include γ-butyrolactone, δ-valerolactone, δ-hexanolactone, ε-caprolactone, γ-valerolactone, γ-hexalactone, γ-heptalactone, γ-octalactone, γ-nonalactone, γ -decalactone, γ-undecalactone, δ-heptalactone, δ-octalactone, δ-nonalactone, δ-decalactone, δ-undecalactone and the like. Among these, γ-butyrolactone, δ-valerolactone, δ-hexanolactone, ε-caprolactone and γ-valerolactone are more preferable, and ε-caprolactone is more preferable. Cyclic carbonate includes propylene carbonate, ethylene carbonate and the like.

The content of the cyclic ester solvent is not particularly limited, but the lower limit of the content of the cyclic ester solvent is preferably in the range of 1% by mass or more, and in the range of 5% by mass or more, based on the total amount of the non-aqueous ink composition. More preferably, it is in the range of 8% by mass or more.

The upper limit of the content of the cyclic ester solvent is preferably 90% by mass or less, more preferably 70% by mass or less, and even more preferably 50% by mass or less in the total amount of the non-aqueous ink composition.

By containing the organic solvent B, the pigment containing the pigment A can be dispersed more effectively, and the storage stability and recovery from cleaning of the non-aqueous ink composition can be improved. Furthermore, the resulting non-aqueous ink composition has a high surface drying property on the base material, resulting in less bleeding of the print and clearer print.

When the organic solvent B contains at least one of an alkylamide solvent, a cyclic amide solvent, and a cyclic ester solvent, the effect is sufficiently exhibited. May be mixed. By mixing two or more types, the balance of storage stability, suitability for members, surface drying property, and cleaning recovery property can be arbitrarily obtained. When two or more types are mixed, the lower limit of the total content of the organic solvent B is preferably in the range of 1% by mass or more, more preferably 5% by mass or more in the total amount of the non-aqueous ink composition. Preferably, it is more preferably in the range of 10% by mass or more. The upper limit of the total content of the organic solvent B is preferably 90% by mass or less in the total amount of the non-aqueous ink composition.

[Organic solvent C]
The organic solvent C is a glycol ether dialkyl-based solvent in which OH groups at both ends of a glycol are alkyl-substituted, and is represented by the following general formula.

R _a —(—OR _b —)—OR _c (2)
(In formula (2), R _a is an optionally branched alkyl group having 1 to 8 carbon atoms, R _b is an alkylene group having 1 to 4 carbon atoms and may be branched, and R _c is , an optionally branched alkyl group having 1 to 8 carbon atoms, and n represents an integer of 1 to 4.)

R1 is preferably an optionally branched alkyl group having 1 to 4 carbon atoms. R2 is preferably an optionally branched alkylene group having 1 to 3 carbon atoms. R3 is preferably hydrogen or an optionally branched alkyl group having 1 to 4 carbon atoms.

Organic solvents represented by formula (2) include, for example, 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, and diethylene glycol dibutyl ether. , diethylene glycol butyl methyl ether, diethylene glycol butyl ethyl ether, diethylene glycol methyl-2-ethylhexyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol ethyl methyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene Glycol 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 Dialkyl ethers of polyhydric alcohols such as 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, tripropylene glycol ethyl methyl ether can be mentioned.

From the viewpoint of the permeability to the substrate onto which the non-aqueous ink composition is discharged, the leveling property on the substrate surface, and the drying property, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dipropyl ether, diethylene glycol Propyl methyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl methyl ether, diethylene glycol butyl ethyl ether, diethylene glycol methyl-2-ethylhexyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol ethyl methyl ether, tetraethylene glycol dimethyl ether, propylene Glycol diethyl ether, propylene glycol ethyl methyl ether, propylene glycol methyl propyl ether, propylene glycol methyl butyl ether, propylene glycol methyl-2-ethylhexyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl methyl ether, dipropylene Glycol methyl propyl ether, dipropylene glycol dipropyl ether, tripropylene glycol dimethyl ether, tripropylene glycol ethyl methyl ether and the like are preferred.

Moreover, it is preferable to combine two or more types of glycol ether solvents having different flash points among these glycol ether solvents. By containing a glycol ether solvent with a high flash point (for example, a flash point of 70° C. or higher), a non-aqueous ink composition having high recovery from cleaning can be obtained. By containing a glycol ether solvent with a low flash point (for example, a flash point of less than 70° C.), a non-aqueous ink composition with high surface drying property on a substrate can be obtained. By containing a glycol ether solvent with a flash point of 70°C or more and a glycol ether solvent with a flash point of less than 70°C, it is possible to achieve both high recovery from cleaning and surface drying on the substrate. , it becomes a non-aqueous ink composition that exhibits the effects of the present invention particularly effectively.

Moreover, it is more preferable to contain an organic solvent B (at least one selected from the group consisting of an alkylamide solvent, a cyclic amide solvent, and a cyclic ester solvent) and an organic solvent C. The storage stability of the non-aqueous ink composition, high recovery from cleaning, and surface drying property on the substrate can be achieved at the same time, and the non-aqueous ink composition particularly exhibits the effects of the present invention.

[Other organic solvents]
The non-aqueous ink composition according to this embodiment may contain an organic solvent other than the above organic solvents. Specific examples include glycol ether monoalkyl in which one OH group of glycol is substituted with alkyl. Glycol ether monoalkyl solvents include, for example, ethylene glycol mono-n-butyl ether, ethylene glycol mono-isobutyl ether, ethylene glycol mono-t-butyl ether, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol monomethyl (or ethyl, propyl , isopropyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl ether, triethylene glycol monomethyl (or ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl) ether, tetraethylene glycol monomethyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-isobutyl ether, propylene glycol mono-t-butyl ether, propylene glycol mono-2-ethylhexyl ether, dipropylene glycol monomethyl (or ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl) ether, tripropylene glycol monomethyl ether (or ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl) ether, tetrapropylene glycol monomethyl ether (or ethyl, propyl, isopropyl, n -butyl, isobutyl, t-butyl, 2-ethylhexyl), and alkylene glycol monoalkyl ethers.

Moreover, other solvents than the glycol ether solvent may be contained. Specifically, oxazolidinone solvents different from the cyclic amide solvents of the above formula (4) such as 3-methyl-2-oxazolidinone, 3-ethyl-2-oxazolidinone, N-vinylmethyloxazolidinone, and 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 and other acetate solvents and 3 -methoxypropanamide, 3-butoxypropanamide, N,N-dimethyl-3-methoxypropanamide, N,N-dibutyl-3-methoxypropanamide, N,N-dibutyl-3-butoxypropanamide, N,N - Amide-based solvents different from the alkylamide-based solvents of the above formula (3) such as dimethyl-3-butoxypropanamide and the cyclic amide-based solvents of the above formula (4), methyl alcohol, ethyl alcohol, n-propyl alcohol, and isopropyl Alkyl alcohols having 1 to 5 carbon atoms such as alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-pentanol; 3-methoxy-3-methyl-1-butanol, 3- monohydric alcohol solvents such as methoxy-1-propanol, 1-methoxy-2-propanol and 3-methoxy-n-butanol; ketones or ketoalcohols such as acetone and diacetone alcohol; ethers such as tetrahydrofuran and dioxane ; oxyethylene or oxypropylene copolymers such as polyethylene glycol and polypropylene glycol; ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-propanediol, isobutylene glycol, triethylene glycol, tripropylene glycol, tetraethylene glycol , 1,3-propanediol, 2-methyl-1,2-propanediol, 2-methyl-1,2-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol , 1,2-pentanediol, 1,2-hexanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl Diols such as -2,4-pentanediol, 3-methyl-1,3-butanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol; glycerin, trimethylolethane , trimethylolpropane, triols such as 1,2,6-hexanetriol: mesoerythritol, tetrahydric alcohols such as pentaerythritol, monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-ethylethanol Alkanolamines such as amines, N-butylethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, and the like. It is preferable to select a solvent with an appropriate HLB value according to the resin, dispersant, etc. to be combined.

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

[Surfactant]
In the non-aqueous ink composition according to the present embodiment, for the purpose of suppressing volatilization of the non-aqueous ink composition in devices such as nozzles and tubes, preventing solidification, and resolubility when solidified, In addition, for the purpose of reducing the surface tension and improving the wettability with the recording medium (substrate), for the purpose of suppressing bleeding of the ink composition on the substrate, and for improving the abrasion resistance of the coating film. A surfactant may be added for the purpose and for the purpose of further improving the glossiness of the recorded matter. Surfactants also include those called surface conditioners, leveling agents, antifoaming agents, and the like.

Among these, the surfactant preferably contains a surfactant having a siloxane skeleton. Pigment A tends to agglomerate in a non-aqueous ink composition and tends to have a large volume average particle size. As a result, the glossiness of the obtained recorded matter may be lowered. By including a surfactant having a siloxane skeleton in the non-aqueous ink composition according to the present embodiment, the glossiness of the obtained recorded matter can be improved even if the pigment A is included. Further, if the non-aqueous ink contains a surfactant having a siloxane skeleton, bleeding of the print is reduced and a recorded matter with improved abrasion resistance can be obtained.

As the surfactant having a siloxane skeleton, it is preferable to use polyester-modified silicone or polyether-modified silicone. Specific examples include BYK-313, 315N, 322, 326, 331, 347, 348, BYK-UV3500 and 3510. , 3530, 3570 (both manufactured by BYK-Chemie Japan) and the like can be used.

Further, the non-aqueous ink composition according to the present embodiment may contain a surfactant different from the surfactant having a siloxane skeleton. For example, polyoxyalkylene alkyl ethers 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.), Adekatol NP-620, NP-650, NP-660, NP-675, NP-683, NP-686, Adekacol CS-141E, TS-230E (manufactured by Adeka Co., Ltd.), Sorgen 30V, 40, TW-20, TW-80, Neugen CX-100 (Daiichi Kogyo Seiyaku Co., Ltd.) It is preferable to use a fluorine-modified polymer as a fluorine-based surfactant, such as BYK-340 (manufactured by BYK-Chemie Japan). , Surfynol (registered trademark) 82, 104, 465, 485, TG (all manufactured by Air Products Japan), Olfin (registered trademark) STG, E1010 (all manufactured by Nissin Chemical Co., Ltd.), and the like. Surfactants are not limited to those described above, and any of anionic, cationic, amphoteric or nonionic surfactants can be used.

The non-aqueous ink composition according to the present embodiment may contain these surfactants together with a surfactant having a siloxane skeleton, or may contain these surfactants without containing a surfactant having a siloxane skeleton. It may contain an agent.

In the non-aqueous ink composition according to the present embodiment, the content of the surfactant is not particularly limited, but the lower limit of the content of the surfactant is preferably in the range of 0.01% by mass or more. It is preferably in the range of 0.05% by mass or more, more preferably in the range of 0.1% by mass or more. The lower limit of the surfactant content is preferably 5.0% by mass or less, more preferably 4.0% by mass or less, and 3.0% by mass or less. is more preferable, and 1.5% or less is even more preferable. When the content of the surfactant is within the above range, it is possible to make the physical properties of the ink film of the printed matter excellent, such as abrasion resistance, solvent resistance, and water resistance.

[Other ingredients]
The non-aqueous ink composition according to the present embodiment includes stabilizers such as antioxidants and ultraviolet absorbers, epoxides and the like, polyvalent carboxylic acids, pH adjusters, bactericides, preservatives, deodorants, and charge adjusters. , wetting agents, and other known additives as optional ingredients. Specific examples of antioxidants include hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, hydrazine-based antioxidants, and the like. Specific examples include BHA (2,3-butyl-4-oxyanisole) and BHT (2,6-di-t-butyl-p-cresol). Moreover, a benzophenone-based compound or a benzotriazole-based compound can be used as the ultraviolet absorber. Specific examples of the epoxidized product include epoxy glyceride, epoxy fatty acid monoester, and epoxy hexahydrophthalate, and specific examples include ADEKA CIZER O-130P and ADEKA CIZER O-180A (manufactured by ADEKA). exemplified. Specific examples of polycarboxylic acids include citric acid and maleic acid.

≪2. Method for producing non-aqueous ink composition>>
The method for producing a non-aqueous ink composition according to the present embodiment can be produced by mixing an organic solvent, a pigment containing Pigment A, and other components (for example, a resin) using a paint shaker. At this time, each component may be dispersed with zirconia beads. In addition, the obtained non-aqueous ink composition may be adjusted to a desired dissolved oxygen content and dissolved nitrogen content by, for example, deaeration treatment, if necessary.

Although the non-aqueous ink composition according to the present embodiment is a non-aqueous ink composition that does not contain water intentionally, water may be mixed in from raw materials or during the manufacturing process. It is desirable that the water content in the non-aqueous ink composition is as low as possible. Excessive water content deteriorates storage stability and dischargeability, and further increases the risk of generation of solid components and the like. The upper limit of the water content in the non-aqueous ink composition is preferably 1.0% by mass or less, particularly preferably 0.5% by mass or less, particularly preferably 0.3% by mass, based on the total amount of the non-aqueous ink composition. More preferably:

At this time, it is preferable to dry the organic solvent in advance. By drying the organic solvent in advance, the amount of water contained in the non-aqueous composition can be reduced. As a method for drying the organic solvent, for example, a method of spraying an inert gas (e.g., nitrogen gas) dried in an inert gas atmosphere such as nitrogen for a predetermined time, a method of distilling and refining the organic solvent, and water are selected. Examples include a method of allowing the organic solvent to permeate through a semi-permeable membrane that selectively permeates the organic solvent, and a method of selectively adsorbing water mixed in the organic solvent with a water adsorbent that adsorbs water.

≪3. Recording Method Using Ink Composition>>
The recording method according to the present embodiment is a recording method in which the above non-aqueous ink composition is ejected onto the surface of a substrate by an inkjet method. The non-aqueous ink composition of the present invention satisfies the properties required for a non-aqueous ink composition ejected by an inkjet method. It satisfies the properties required for water-based ink compositions. A method of ejecting ink by an inkjet method may be a piezo method using a piezoelectric element or a thermal method using a heating element, and is not particularly limited.

≪4. Method for producing recorded matter≫
A recording method using the above ink composition can also be defined as a method for producing a recorded matter. The method for producing a recorded matter according to the present embodiment also satisfies the properties required for a non-aqueous ink composition ejected by an inkjet method.

≪5. Records≫
Each layer constituting the recorded matter manufactured by the method for manufacturing the recorded matter of the above-described embodiment will be described.

[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. Various substrates can be used, including absorbent substrates such as fabrics, and substrates with surface coatings such as substrates having a receiving layer.

Among these, since the non-aqueous ink composition is a non-aqueous ink composition that does not contain water, it is preferable that the surface is mainly made of a resin. In particular, when the above non-aqueous ink composition contains an alkylamide solvent, bleeding of printing on a medium (recording medium) whose surface is made of a resin is reduced, resulting in clear printing. Examples of resins include polyvinyl chloride-based polymers, acryl, PET, polycarbonate, PE, and PP. Further, it may be used for a resin base material (so-called resin base material for lamination) on the premise that a film is attached to the recording surface of a recorded matter. In particular, a base material (recording medium) whose surface is made of a hard or soft polyvinyl chloride polymer is preferred. Examples of the substrate (recording medium) whose surface is made of a polyvinyl chloride polymer include polyvinyl chloride substrates (films or sheets).

[Recording layer]
The recording layer is a layer formed by volatilization of the solvent contained in the non-aqueous ink composition, and is a layer that forms a desired image. By ejecting the above non-aqueous ink composition, the characteristics required for the non-aqueous ink composition ejected by the inkjet method are satisfied.

[Other layers]
The recorded matter according to this embodiment may further include a layer having a desired function on the upper surface of the recording layer. For example, an overcoat layer containing at least one of resin and wax may be formed for the purpose of further imparting abrasion resistance and glossiness to the recorded matter. Further, a layer having an uneven surface (a matte surface) may be formed by adding a filler or changing the film thickness for each pixel. Moreover, in order to impart weather resistance to the recorded matter, a weather resistant layer containing an ultraviolet absorber, a light stabilizer, etc., a glittering layer containing a glittering pigment, or the like may be formed.

≪6. Ink set≫
The ink set according to the present embodiment is an ink set comprising at least the above non-aqueous ink composition. For example, when the non-aqueous ink composition is an orange ink, the effect of the present invention can be obtained by combining a conventionally known yellow ink, magenta ink, cyan ink, and black ink. It becomes possible to expand the color reproducibility.

Further, an ink set containing the above non-aqueous ink composition and glittering ink such as white ink, metallic ink, or pearl ink may be used. Also, an ink set containing the above non-aqueous ink composition, clear ink, pre-coating ink, overprint ink, or the like may be used.

≪7. Inkjet recording device≫
The above non-aqueous ink composition satisfies the properties required as a non-aqueous ink composition ejected by an inkjet method even when a pigment containing a perinone pigment is used as the pigment. By ejecting onto the surface of the substrate by an inkjet method using an inkjet recording device equipped with an ink cartridge (corresponding to a container) filled with a substance, the glossiness of the printed surface of the resulting printed matter can be improved. It becomes possible to satisfy the properties required as a non-aqueous ink composition.

A conventionally known one can be used for this ink jet recording apparatus. For example, an inkjet printer such as VersaArt RE-640 manufactured by Roland DG Co., etc. can be used.

As an example of the configuration of the inkjet recording apparatus, an on-carriage type and serial printer type inkjet recording apparatus will be described. It may be an off-carriage type inkjet recording device fixed to the head, or a line printer type inkjet recording device in which the ink composition is ejected onto the recording medium (substrate) without moving the inkjet head. good.

Also, the inkjet recording apparatus preferably includes a heating mechanism and a fixing mechanism for fixing the substrate. The organic solvent contained in the non-aqueous ink composition is dried by controlling the substrate surface temperature with a heating mechanism provided in the inkjet recording apparatus and drying the non-aqueous ink composition that has landed on the substrate (recording medium). can be volatilized.

Furthermore, the fixing mechanism for fixing the base material makes it possible to dry the non-aqueous ink composition while the base material (recording medium) is fixed. Uniformity can be suppressed. This makes it possible to effectively dry the non-aqueous ink composition that has landed on the substrate (recording medium).

The heating mechanism provided in the inkjet recording apparatus may be a pre-heater, a platen heater, an after-heater, or the like, or may be a mechanism for blowing warm air onto the recorded matter. Also, a plurality of these heating mechanisms may be combined.

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

A fixing mechanism for fixing the substrate may be a fixing mechanism for fixing the substrate with a predetermined jig, or a fixing mechanism for sucking and adsorbing the substrate by negative pressure, and is not particularly limited.

The inkjet head for ejecting the non-aqueous ink composition may be a piezoelectric inkjet head using a piezoelectric element or a thermal inkjet head using a heating element, and is not particularly limited.

In addition, the inkjet recording apparatus includes a plastic tube connecting a container (ink cartridge, bottle, etc.) for storing the non-aqueous ink composition and an inkjet ejection port for ejecting the non-aqueous ink composition. A non-aqueous ink composition may be supplied to the inkjet head through this plastic tube and ejected by an inkjet method.

Moreover, it is preferable that the tube connected to the storage mechanism and the inkjet ejection port has a valve mechanism for adjusting the flow path of the non-aqueous ink composition. By supplying the non-aqueous ink composition from the storage mechanism to the inkjet ejection port through the valve mechanism, a mechanism capable of eliminating nozzle clogging is provided, and the ejection stability of the non-aqueous ink composition can be further improved. can.

As described above, the ink jet recording apparatus according to the present embodiment can use inks of various colors such as yellow, magenta, cyan, and black, light magenta, light cyan, light black, orange, green, red, white, metallic, and pearl ink. , clear, pre-coating, overprinting, etc., and the order of colors to be printed and 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 have a winding mechanism for the recording medium (base material), a drying mechanism for drying the surface of the base material, and an ink circulation mechanism.

The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these descriptions.

1. Preparation of non-aqueous ink composition Organic solvent, resin, dispersant, pigment (coloring material) Non-aqueous ink compositions of Examples and Comparative Examples were prepared according to the proportions of each component shown in the table below. Specifically, using a paint shaker, zirconia beads were dispersed until the volume-based cumulative 90% particle diameter D90 was 450 nm or less to prepare a non-aqueous ink composition. The unit is % by mass.

The volume-based cumulative 90% particle size D90 of the pigment contained in the non-aqueous ink composition was measured using a particle size distribution analyzer (particle size analyzer NANOTRACWAVE manufactured by Microtrack Bell Co., Ltd.).

2. Evaluation (discharge stability)
Ejection stability was evaluated for the non-aqueous ink compositions of Examples, Comparative Examples, and Reference Examples. Specifically, an inkjet printer (trade name VersaArt RE-640, manufactured by Roland DG Co., Ltd. is used) is filled with a non-aqueous ink composition, and a recording medium (polyvinyl chloride film with glue (IMAGin JT5829R: MACtac )) in a bi-directional high-speed printing mode (360 x 720 dpi) at a base material surface temperature of 40 ° C. Print solid and fine lines by continuous printing, and visually observe the presence or absence of missing dots, flight bending, and ink splattering. It was evaluated (indicated as "discharge stability" in the table).
Evaluation Criteria A: Fine lines are correctly reproduced.
B: A fine line is generally correctly reproduced, although a slight shift in the landing position is observed.
C: A fine line cannot be reproduced due to deviation of the landing position.
A and B are within the usable range.
(Storage stability)
Storage stability was evaluated for the non-aqueous ink compositions of Examples and Comparative Examples. Specifically, the non-aqueous ink composition was sealed in a glass bottle and stored at 60° C. for one month, and the rate of change in viscosity from before storage was determined. The viscosity of the ink was measured at 20° C. using a falling ball viscometer (AMVn manufactured by Anton Paar).
A: The rate of change is less than 10%.
B: The rate of change is 10% or more and less than 20%.
C: The rate of change is 20% or more.
A and B are within the practical usable range.

(chromogenic)
The non-aqueous ink compositions of Examples and Comparative Examples were evaluated for color development. Specifically, high-quality printing is performed on a recording medium (polyvinyl chloride film with glue (IMAGin JT5829R: manufactured by MACtac)) using the inkjet printer (trade name: VersaArt RE-640, manufactured by Roland DG Co., Ltd.). A solid image was printed in mode (1440×720 dpi). The chroma was measured based on JIS Z 8721 using X-Rite eXact (manufactured by X-Rite) under the conditions of a viewing angle of 2°, a measurement range of 4 mmφ, and a D65 light source. (Indicated as "chromogenicity" in the table).
Evaluation Criteria A: Saturation is 90 or more.
B: Saturation is 70 or more and less than 90.
C: Saturation is less than 70.
A and B are within the practical usable range.

(glossiness)
Glossiness was evaluated for the non-aqueous ink compositions of Examples, Comparative Examples and Reference Examples. Specifically, a printed matter was prepared in the same manner as in the evaluation of color developing properties, and the 20° glossiness of the printed matter was measured using a handy type gloss meter Phopoint IQ-S (manufactured by Konica Minolta). (Indicated as "glossiness" in the table).
Evaluation Criteria A: 20° gloss of 60 or more B: 20° gloss of 55 or more and less than 60 C: 20° gloss of less than 55 A and B are within the practical usable range.

(Scratch resistance)
The non-aqueous ink compositions of Examples, Comparative Examples and Reference Examples were evaluated for scratch resistance. Specifically, a printed matter was prepared in the same manner as in the evaluation of color development and glossiness, and the printed surface of the printed matter was rubbed with a dry cotton cloth with a load of 200 g and 50 reciprocations, and the abrasion resistance was visually evaluated.
Evaluation Criteria A: No trace of rubbing was observed on the printed surface.
B: The print surface was slightly rubbed, but substantially within the allowable range.
C: Clear peeling was observed on the printed surface.
A and B are within the practical usable range.

(solvent resistance)
The non-aqueous ink compositions of Examples, Comparative Examples and Reference Examples were evaluated for solvent resistance. Specifically, the printed surface of the printed material was rubbed with a cotton cloth impregnated with a 50% by mass aqueous alcohol solution at a load of 200 g, 50 reciprocations, and the abrasion resistance was visually evaluated in the same manner as in the above abrasion resistance evaluation.
Evaluation Criteria A: No trace of rubbing was observed on the printed surface.
B: The print surface was slightly rubbed, but substantially within the allowable range.
C: Clear peeling was observed on the printed surface.
A and B are within the practical usable range.

In the table, "PO43-a" is "A-76" manufactured by Arimoto Chemical Industry Co., Ltd. (Pigment A represented by formula (1), which is a perinone pigment).

In the table, "PO43-b" is "Hostaperm Orange GR" manufactured by Clariant (a perinone-based pigment which is a pigment A represented by formula (1)).

In the table, "PO43-c" is a pigment synthesized by the method described in Japanese Patent No. 3076738 (Pigment A represented by Formula (1), which is a perinone pigment).

In the table, "PB15:4" means C.I. I. Pigment Blue 15:4.

In the table, "PR122" means C.I. I. Pigment Red 122.

In the table, "PY150" means C.I. I. Pigment Yellow 150.

In the table, "CB" is carbon black.

In the table, "Dispersant-a" is "Solsperse 32000" (polycaprolactone-based polymer dispersant, amine value: 35 mgKOH/g) manufactured by Lubrizol.

In the table, "dispersant-b" is "Solsperse 33000" (polycaprolactone-based polymer dispersant, amine value: 43 mgKOH/g) manufactured by Lubrizol.

In the table, "dispersant-c" is "Solsperse 36000" (polycaprolactone-based polymer dispersant) manufactured by Lubrizol.

In the table, "Resin-a" is "Paraloid B60" (acrylic resin) manufactured by Rohm and Haas.

In the table, "Resin-b" is "Solbin CL" (vinyl chloride-vinyl acetate copolymer resin) manufactured by Nissin Chemical Industry Co., Ltd.

In the table, "Resin-c" is "CAB551-0.01" (cellulose resin) manufactured by EASTMAN.

In the table, "Surfactant-a" is "BYK-331" (polyester-modified silicone or polyether-modified silicone) manufactured by BYK-Chemie Japan.

In the table, "Surfactant-b" is "BYK-3500" (polyester-modified silicone or polyether-modified silicone) manufactured by BYK-Chemie Japan.

As can be seen from the above table, if the non-aqueous ink composition of the example containing the pigment A (perinone pigment) represented by formula (1) and the content of the pigment dispersant is less than the content of the pigment, , satisfies the characteristics required as a non-aqueous ink composition ejected by an inkjet method.

On the other hand, the non-aqueous ink composition of the comparative example, which contains the pigment A (perinone pigment) represented by formula (1) and the content of the pigment dispersant is equal to or greater than the content of the pigment, has a The glossiness of the ink composition is lowered, and the abrasion resistance and solvent resistance are also lowered.

The non-aqueous ink compositions of Reference Examples 1 to 4, which do not contain the pigment A (perinone pigment) represented by formula (1), can be obtained by the inkjet method even if the content of the pigment dispersant is equal to or greater than the content of the pigment. It satisfied the characteristics required as a non-aqueous ink composition ejected by. From this, the problem of the present invention that the pigment aggregates in the non-aqueous ink composition is unique to the non-aqueous ink composition containing the pigment A (perinone pigment) represented by formula (1). was confirmed.

Claims (13)

A non-aqueous ink composition ejected by an inkjet method containing a pigment, a pigment dispersant, an organic solvent, and a resin different from the pigment dispersant and the surfactant ,
The pigment contains a pigment A represented by the following formula (1),
The content of the pigment dispersant is smaller than the content of the pigment,
The content of the resin is greater than the content of the pigment,
Non-aqueous ink composition.

(In the formula (1), each of X1 to X12 is independently a hydrogen atom, a halogen atom, an optionally branched alkyl group having 1 to 5 carbon atoms, or an aromatic hydrocarbon group optionally substituted with a hydrogen atom. , a cyano group, a nitro group, an amino group, -OH, -COOH, -COO-M ⁺ , -SO ₃ H, -SO ₃ ^- M ⁺ , a phthalimido group optionally substituted with a hydrogen atom, a phthalimidomethyl group, or a heterocyclic compound, and M ⁺ indicates a cation.) The content of the pigment is 1.0% by mass or more,
The non-aqueous ink composition according to claim 1 . The content of the resin is greater than the content of the pigment dispersant,
The non-aqueous ink composition according to claim 1 or 2 . (content of the pigment dispersant) / (content of the resin) is less than 0.8,
The non-aqueous ink composition according to any one of claims 1 to 3 . The content of the resin is greater than the total content of the pigment and the pigment dispersant,
The non-aqueous ink composition according to any one of claims 1 to 4 . The content of the resin is greater than the total content of the pigment, the pigment dispersant, and the surfactant.
The non-aqueous ink composition according to any one of claims 1 to 5 . (total content of the pigment dispersant and the surfactant)/(content of the resin) is 0.3 or more and less than 1.0,
The non-aqueous ink composition according to claim 6 . The content of water in the ink composition is 0.5% by mass or less.
The non-aqueous ink composition according to any one of claims 1 to 7 . 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. 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,
A method for producing a recorded matter. At least comprising the non-aqueous ink composition according to any one of claims 1 to 8 ,
ink set. A printed layer of the non-aqueous ink composition according to any one of claims 1 to 8 is formed on the surface of a substrate,
Records. A storage container filled with the non-aqueous ink composition according to any one of claims 1 to 8 is mounted,
Inkjet recording device.