JP2023133065A - Non-aqueous ink composition, ink set, recording method using the same, method for producing recorded matter, recorded matter and inkjet recording device - Google Patents

Abstract

To provide a non-aqueous ink composition which can be suitably used as a non-aqueous ink composition discharged by an inkjet method even if the non-aqueous ink composition comprises a perinone-based pigment.SOLUTION: There is provide a non-aqueous ink composition which comprises a pigment, a pigment dispersant, an organic solvent and a resin and is discharged by an inkjet method, wherein the pigment includes a pigment A represented by the following formula (1) and the content of the pigment dispersant is smaller than the content of the pigment. (wherein, X1 to X12 each independently represent hydrogen, a halogen atom, an alkyl group, an aromatic hydrocarbon group, a cyano group, a nitro group, an amino group, -OH, -COOH, -COO-M+, -SO3H, -SO3-M+ or the like and M+ represents a cation.)SELECTED DRAWING: 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.

Ink compositions include 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. 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. According to Patent Document 1, it is described that this aqueous ink composition has good storage stability by containing a perinone pigment and an azo compound.

Japanese Patent Application Publication No. 2012-172070

Since perinone pigments have weather resistance, ink compositions containing perinone pigments are particularly suitable for producing recorded materials to be used outdoors.

However, non-aqueous ink compositions containing perinone pigments tend to have poor ejection properties and storage stability, and are difficult to eject using the inkjet method, resulting in poor print surface gloss and coating film resistance. The inventor's research has revealed that there are cases where the characteristics required for a non-aqueous ink composition are not satisfied.

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

As a result of intensive studies to solve the above problems, the present inventors discovered that the above problems could be solved by controlling the content of the pigment and pigment dispersant within a predetermined range, and thus completed the present invention. Ta. 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 pigment A represented by the following formula (1),
The content of the pigment dispersant is smaller than the content of the pigment,
Non-aqueous ink composition.

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

(2) the content of the resin is greater than the content of the pigment;
The non-aqueous ink composition described in (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 based on 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 discharging the non-aqueous ink composition according to any one of (1) to (10) onto the surface of a substrate using an inkjet method.

(12) A method for producing a recorded matter, comprising discharging the non-aqueous ink composition according to any one of (1) to (10) onto the surface of a substrate using 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 base material.

(15) An inkjet recording device 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 characteristics required for a non-aqueous ink composition discharged by an inkjet method even if a pigment including a penolin pigment is used as a pigment.

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 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 that is ejected by an inkjet method and contains a pigment, a pigment dispersant, an organic solvent, and a resin. Here, the term "non-aqueous ink composition" refers to an ink composition containing an organic solvent that is manufactured without intentionally containing water, unlike an aqueous ink composition whose main component is water. means.

The pigment contained in this non-aqueous ink composition contains 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 pigments contained in it.

（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 formula (1), X1 to X12 are substituents containing hydrogen. Aromatic hydrocarbon group which may be substituted, cyano group, nitro group, amino group, -OH, -COOH, -COO ^- M ⁺ , -SO ₃ H, -SO ₃ ^- M ⁺ , hydrogen atom is substituted represents a phthalimide group, a phthalimidomethyl group, or a heterocyclic compound that may be conjugated, and M ⁺ represents a cation.)

The content of the pigment dispersant is smaller than the content of the pigment (less than the content of the pigment), which improves the glossiness and coating resistance of the print surface of the resulting printed matter. It becomes possible to satisfy the characteristics required of 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, non-aqueous inkjet compositions containing this pigment tend to have relatively easy dispersibility of the pigment and deteriorate storage stability upon contact with water. By reducing the water content in a non-aqueous ink composition to avoid containing water as much as possible (intentionally not containing water), storage stability, cleaning recovery properties, etc. can be improved. becomes possible.

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

[Pigment]
The non-aqueous ink composition according to this embodiment contains a pigment. This pigment is characterized by containing 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 formula (1), X1 to X12 are each independently hydrogen, a halogen atom, an optionally branched alkyl group having 1 to 5 carbon atoms, and an optionally hydrogen-substituted aromatic hydrocarbon group) , cyano group, nitro group, amino group, -OH, -COOH, -COO-M ⁺ , -SO ₃ H, -SO ₃ ^- M ⁺ , phthalimide group where hydrogen atom may be substituted, phthalimidomethyl group, or a heterocyclic compound, and M ⁺ represents a cation.)

Since such Pigment A has weather resistance, it is possible to improve the weather resistance of printed matter obtained with a non-aqueous ink composition containing Pigment A. Moreover, since the content of the pigment dispersant is smaller than the content of the pigment, it becomes possible to satisfy the characteristics required for a non-aqueous ink composition discharged by an inkjet method.

The 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 types of substituents (X1 to X12) includes a method of dispersing the pigment in an organic solvent and introducing a desired substituent using an additive capable of introducing a specific substituent. For example, it can be prepared by the method described in Japanese 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 used. There are no limitations, and the number of substituents is not particularly limited either.

The average particle diameter of pigment A is not particularly limited, but the upper limit of the volume-based cumulative 90% particle diameter 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 inkjet dischargeability is improved, and the ink composition can be more suitably used as a non-aqueous ink composition to be discharged by an inkjet method. The lower limit of the volume-based cumulative 90% particle diameter D90 is preferably 50 nm or more, and preferably 100 nm or more. When the volume-based cumulative 90% particle diameter D90 of pigment A is within 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 is 90%. The "volume-based cumulative 90% particle size D90" can be measured using a particle size distribution measuring device (such as the particle size analyzer NANOTRACWAVE manufactured by Microtrack Bell Co., Ltd. or the particle size measuring device FPAR-1000 manufactured by Otsuka Electronics Co., Ltd.). ) 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, and preferably 0.3% by mass or more based on the total amount of the non-aqueous ink composition. More preferably, it is 0.5% by mass or more, even 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 preferable. When the content of 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 that can be obtained by combining with non-aqueous ink compositions of other colors. The color reproduction range of objects can be increased. Further, 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. By setting the content of Pigment A to 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 additive materials, and the dispersion stability of Pigment A improves. Further, since an increase in viscosity due to an increase in the content of pigment A can be suppressed, nozzle clogging of an inkjet head can be suppressed.

As the pigment A represented by formula (1), C. I. Pigment Orange 43 may be mentioned. Pigment A represented by formula (1) may be synthesized, for example, commercially available C. I. Pigment Orange 43 can be washed with a solution (acid solution, alkaline solution, or neutral solution) to treat the surface of the pigment, or the substituents (X1 to It may be obtained by changing the type of X12) or by processing both. Commercially available products include A-76 manufactured by Arimoto Chemical Co., 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. List It will be done.

Further, the non-aqueous ink composition according to the present embodiment may further contain coloring materials (including pigments and dyes) other than the above-mentioned pigment A. Such coloring materials include pigments and dyes with hues similar to pigment A (for example, 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 the above-mentioned pigment A using color index (C.I.) numbers 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. 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 Brown 23, 25, 26, etc.

In the total amount of pigments contained in the non-aqueous ink composition, the content of the above-mentioned pigment A is preferably 50% by mass or more, more preferably 70% by mass or more, and preferably 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 in that the content of the pigment dispersant is smaller than the content of the pigment contained in the non-aqueous ink composition. This makes it possible to suppress the aggregation of the perinone pigment contained in the non-aqueous ink composition, and improves the glossiness of the printed surface of the resulting printed matter. 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 based on 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 preferably 0.3% by mass or more based on the total amount of the non-aqueous ink composition. It is more preferably at least 0.5% by mass, particularly preferably at least 1.0% by mass.

As the pigment dispersant, any dispersant used in non-aqueous ink compositions can be used. As the pigment dispersant, it is preferable to use a polymer dispersant. As a polymeric dispersant, the main chain is made of polyester, polyacrylic, polyurethane, polyamine, polycaprolactone, etc., and the side chain has polar groups such as amino, carboxyl, sulfone, and hydroxyl groups. It is something. Among these, by using a polymeric dispersant containing a polycaprolactone-based polymeric dispersant, it is possible to more effectively suppress agglomeration of perinone-based pigments contained in non-aqueous ink compositions. .

For Pollykril -based dispersing agents, for example, DISPERBYK -20000, 2001, 2008, 209, 2020, 2020n, 2025, 2025, 2070, 2070, 2150, 2155, 2164, BYKJET -91, BYKJET -91. 30, 9131 , 9132, 9133, 9151 (manufactured by Bic Chemie), EfkaPX4310, 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.), Florene DOPA-15BHFS, 17HF, 22, G-700, 900, NC-500, GW-1500 (manufactured by Kyoeisha Chemical Co., Ltd.), etc. are used. Examples of polycaprolactone dispersants include Ajisper PB821, PB822, PB881 (manufactured by Ajinomoto Fine Techno Co., Ltd.), Hinoact KF-1000, T-6000, T-7000, T-8000, T-8000E, T-9050 ( Kawaken Fine Chemical Co., Ltd.), Solsperse20000, 24000, 32000, 32500, 32550, 32600, 33000, 33500, 34000, 35200, 36000, 37500, 39000, 71000, 76400, 76500, 8600 0, 88000, J180, J200 (Lubri TEGO Dispers 652, 655, 685, 688, 690 (manufactured by Evonik Japan), etc. are used. Preferred dispersants include BYKJET-9130, 9131, 9132, 9133, 9151, EfkaPX4310, PX4320, PX4330, PX4700, PX4701, Solsperse20000, 24000, 32000, 33000, 33500, 34000. , 35200, 39000, 71000, 76500, 86000, 88000, J180, J200, TEGO Dispers 655, 685, 688, 690, etc. are used. These can be used alone or in combination.

In particular, when substituents (X1 to X12) in the benzene ring in the molecular structure of Pigment A are introduced with substituents that exhibit acidity to weak basicity, pigment dispersants having basic groups among the above can be used. It is preferable to use By using a pigment dispersant having a basic group, aggregation of pigment A in the non-aqueous ink composition can be suppressed.

Among these, it is preferable to use a pigment dispersant having an amine value 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. In particular, when the pH of Pigment A is 8 or lower (preferably when the pH is 7 or lower), a pigment dispersant with an amine value within a predetermined range is more likely to adhere to the surface of Pigment A, so non-aqueous ink It becomes possible to effectively suppress aggregation of pigment A in the composition.

Further, 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. It becomes possible to effectively suppress the aggregation of pigment A by using a high molecular weight pigment dispersant, and it becomes possible to effectively suppress the aggregation of pigment A in a non-aqueous ink composition. It becomes possible to make it have good storage stability. Furthermore, it is possible to improve the coating film resistance of printed matter.

[Dispersion aid]
A dispersion aid may be used in the non-aqueous ink composition according to the present embodiment, if necessary. The dispersion aid is adsorbed on the surface of the coloring material (pigment), and its functional group increases the affinity with the organic solvent and dispersant in the non-aqueous ink composition, thereby improving dispersion stability. As the dispersion aid, derivatives of the pigments described above are preferred, and known pigment derivatives having functional groups such as acidic groups, basic groups, and neutral groups in organic pigment residues 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, the inclusion of the resin makes it possible to suppress aggregation of the perinone pigment contained in the non-aqueous ink composition. It becomes possible to satisfy the characteristics required for a non-aqueous ink composition discharged by an inkjet method, such as improved scratch resistance on the printed surface. Furthermore, by containing the resin, the fixing properties, 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, phenolic resin, terpene resin, polyamide resin, vinyltoluene-α-methylstyrene copolymer, ethylene-vinyl acetate copolymer, cellulose acetate butyrate, cellulose acetate propionate, silicone (silicon) type resins, acrylamide type resins, epoxy type resins, or copolymer resins or mixtures thereof. Among these, those containing acrylic resin, vinyl chloride resin, cellulose resin, polyester resin, and polyurethane resin are preferred.

The acrylic resin is not particularly limited as long as it is included as a main component of the monomer constituting the (meth)acrylic acid ester monomer. The acrylic resin may be a homopolymer of one type of radically polymerizable monomer or a copolymer of two or more selected radically polymerizable monomers. The acrylic resin preferable for the non-aqueous ink composition according to the embodiment is selected from the group consisting of a polymer of methyl methacrylate alone, methyl methacrylate, butyl methacrylate, ethoxyethyl methacrylate, and benzyl methacrylate. It is a copolymer with at least one or more compounds. 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 made of vinyl chloride monomers or a copolymer made of two or more selected polymerizable monomers. Examples of the vinyl chloride resin copolymer include vinyl chloride-vinyl acetate copolymer resin. Vinyl chloride-vinyl acetate copolymer resin is a polymer of vinyl chloride monomer and vinyl acetate monomer. Examples of the vinyl chloride vinyl acetate copolymer resin include vinyl chloride vinyl acetate copolymer, vinyl chloride/vinyl acetate/maleic acid copolymer, vinyl chloride/vinyl acetate/vinyl alcohol copolymer, and vinyl chloride/vinyl acetate. /hydroxyalkyl acrylate copolymers, etc., and mixtures thereof. The vinyl chloride vinyl acetate copolymer resins include "Solvine 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.

Vinyl chloride-vinyl acetate copolymer resin can be obtained by polymerizing vinyl chloride monomer and vinyl acetate monomer. The polymerization method may be any conventionally known polymerization method. The polymerization method is preferably emulsion polymerization or suspension polymerization, and more preferably suspension polymerization.

A cellulose resin is a resin having a cellulose skeleton obtained by biologically or chemically introducing functional groups into cellulose as a raw material. For example, cellulose resins include cellulose acetate alkylate resins such as cellulose acetate butyrate resins, cellulose acetate propionate resins, cellulose acetate propionate butyrate resins, cellulose acetate resins, nitrocellulose resins, and mixtures thereof. Can be mentioned. Examples of the cellulose resins mentioned above include EASTMAN's "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," and other product names.

The polyester resin contains at least a structural unit obtained by polycondensing an alcohol component and a carboxylic acid component. The polyester resin may include a modified polyester resin. Examples of polyester resins include Toyobo's "VYLON226," "VYLON270," "VYLON560," "VYLON600," "VYLON630," "VYLON660," "VYLON885," "VYLONGK250," "VYLONGK810," and "VYLON G. K890” etc. It can be obtained and used under the product names of Unitika, such as "elitle UE-3200", "elitle UE-3285", "elitle UE-3320", "elitle UE-9800", and "elitle UE-9885".

The polyurethane resin contains at least a structural unit obtained by copolymerizing an alcohol component and an isocyanate component. The polyurethane resin may include a polyurethane resin modified with polyester, polyether, or caprolactone. Examples of the above polyurethane resins include Arakawa Chemical Industries' "Yuliano KL-424", "Yuliano KL-564", "Yuliano KL-593", "Yuliano 3262", and DIC's "Pandex 372E", " "Pandex 390E", "Pandex 394E", "Pandex 304", "Pandex 305E", "Pandex P-870", "Pandex P-910", "Pandex P-895", "Pandex It can be obtained and used under trade names such as "4030" and "Pandex 4110."

In addition, these acrylic resins, vinyl chloride resins, cellulose resins, polyester resins, and polyurethane resins may be used alone, but it is preferable to use a mixture of two types. It is more preferable to use a resin that is a mixture of a resin and a vinyl chloride resin. The content ratio of the acrylic resin and the vinyl chloride resin can be controlled to satisfy the requirements for color development, drying properties, coating film properties, printing suitability, etc. required of non-aqueous ink compositions. When mixing an acrylic resin and a vinyl chloride resin, the mixing ratio is not particularly limited and can be changed as appropriate.

Further, the weight average molecular weight of these resins is preferably 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 becomes possible to improve the abrasion resistance of the printed surface of the obtained printed matter. When the resin molecular weight is expressed as an 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 obtained printed matter can satisfy the characteristics required for a non-aqueous ink composition discharged 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 it is preferably contained in a range of 0.05% by mass or more based on the total amount of the non-aqueous ink composition; The content is more preferably 0.1% by mass or more, and even more preferably 0.5% by mass or more. Thereby, the surface drying property of the obtained recorded material can be further improved. The resin contained in the non-aqueous ink composition is preferably contained in an amount 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 that the content is 10.0% by mass or less. Thereby, clogging in the nozzles of the inkjet head can be more effectively eliminated, and the storage stability of the non-aqueous ink composition can be improved.

The content of the pigment dispersant is preferably smaller than the total pigment content. Moreover, it is preferable that the content of the pigment dispersant is smaller than the content of the pigment A. This further improves the glossiness of the printed surface of the resulting printed matter, as well as providing excellent color development, scratch resistance, and solvent resistance, properties required of a non-aqueous ink composition discharged by the inkjet method. This will further satisfy the following. The ratio of the pigment dispersant content to the total pigment or pigment A content in the non-aqueous ink composition (pigment dispersant/total pigment, pigment dispersant/pigment A) is preferably less than 1.0. It is more preferably less than 0.8, even more preferably less than 0.7, and particularly preferably less than 0.6. The lower limit value is preferably 0.1 or more, more preferably 0.2 or more, and even more preferably 0.3 or more.

Preferably, the resin content is 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 pigment dispersant content to the total pigment or pigment A content in the non-aqueous ink composition (pigment dispersant/total pigment, pigment dispersant/pigment A) is preferably less than 1.0. It is more preferably less than 0.8, even more preferably less than 0.7, and particularly preferably less than 0.6. The lower limit is preferably 0.3 or more, more preferably 0.4 or more.

Further, the content of the resin is preferably greater than the content of the pigment dispersant contained in the non-aqueous ink composition. This further improves the glossiness of the printed surface of the resulting printed matter, as well as providing excellent color development, scratch resistance, and solvent resistance, properties required of a non-aqueous ink composition discharged by the inkjet method. This will further satisfy the following.

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. , less than 0.7 is more preferred, less than 0.6 is particularly preferred, and less than 0.4 is most preferred. The lower limit value 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 content of the resin is preferably larger than the total content of the pigment (or pigment A) and the pigment dispersant. This further improves the glossiness of the printed surface of the resulting printed matter, as well as providing excellent color development, scratch resistance, and solvent resistance, properties required of a non-aqueous ink composition discharged by the inkjet method. This will further satisfy the following. 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: It is preferably less than 1.0, more preferably less than 0.95, and even more preferably less than 0.9. 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 content of the resin 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 content of the resin is preferably larger than the total content of the pigment dispersant and the surfactant. The ratio of the total content of pigment dispersant and surfactant to the content of resin in the non-aqueous ink composition ((pigment dispersant + surfactant)/resin) is less than 1.0. It is preferably less than 0.8, more preferably less than 0.6. The lower limit value 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 larger than the total content of the pigment dispersant and the surfactant. The ratio of the total content of pigment dispersant and surfactant to the content of 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 value 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 the present embodiment. The organic solvent is not particularly limited, but from the viewpoint of dispersing the pigment containing pigment A and more effectively achieving the effects of the present invention, organic solvent B (alkylamide solvent, cyclic amide solvent, and cyclic ester) is used. It is preferable to contain at least one selected from the group consisting of solvents. Further, from the viewpoint of improving the ejection properties of the non-aqueous ink composition and more effectively achieving the effects of the present invention, it is preferable to contain an organic solvent C (glycol ether dialkyl solvent).

The alkylamide solvent, cyclic amide solvent, and cyclic ester solvent contained in organic solvent B will be explained below.

[Organic solvent B]
(1) Alkylamide-based solvents Alkylamide-based solvents are compounds that have an alkyl group (C _n H _2n+1 -) and a -C(=O)-N- group (amide bond), and which have hydrogen or alkyl groups. It is a solvent consisting of a compound composed of a -C(=O)-N- group. As the alkylamide solvent, for example, those having the following structure 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.

Note that R ₂ and R ₃ in formula (3) are preferably an alkyl group having 1 or more and 4 or less carbon atoms, and more preferably an alkyl group having 2 or more and 4 or less carbon atoms.

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

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

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

(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. As the cyclic amide solvent, for example, those having 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 the cyclic amide solvent 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 solvent is not particularly limited, but the lower limit of the content of the cyclic amide solvent is preferably in the range of 1% by mass or more based on the total amount of the non-aqueous ink composition, and in the range of 5% by mass or more. It is more preferable that the content be 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 based on the total amount of the non-aqueous ink composition.

(3) Cyclic ester solvent Examples of the solvent having a cyclic ester structure include cyclic carbonate ester solvents and lactone solvents. As the lactone solvent, for example, those 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 is 4 carbon atoms. An alkylene group having 5 or less carbon atoms 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 preferred, and ε-caprolactone is more preferred. Examples of the cyclic carbonate include propylene carbonate and ethylene carbonate.

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 based on the total amount of the non-aqueous ink composition, and in the range of 5% by mass or more. It is more preferable that the content be 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 based on the total amount of the non-aqueous ink composition.

By containing organic solvent B, it becomes possible to more effectively disperse the pigment containing pigment A, and it is possible to improve the storage stability and cleaning recovery properties of the non-aqueous ink composition. Furthermore, the non-aqueous ink composition has high surface drying properties on the substrate, resulting in less blurring and clearer printing.

Organic solvent B exhibits sufficient effects when it contains at least one of an alkylamide solvent, a cyclic amide solvent, and a cyclic ester solvent, but it is effective if it contains at least one of the following: an alkylamide solvent, a cyclic amide solvent, and a cyclic ester solvent; May be mixed. By mixing two or more types, it is possible to achieve an arbitrary balance among storage stability, suitability for parts, surface drying properties, and cleaning recovery properties. When two or more types are mixed, the lower limit of the total content of organic solvent B is preferably 1% by mass or more, more preferably 5% by mass or more based on the total amount of the non-aqueous ink composition. The content is preferably 10% by mass or more, and more preferably 10% by mass or more. The upper limit of the total content of organic solvent B is preferably 90% by mass or less based on the total amount of the non-aqueous ink composition.

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

R _a -(-O-R _b -)-O-R _c ...(2)
(In formula (2), R _a is an optionally branched alkyl group having 1 to 8 carbon atoms, R _b is an optionally branched alkylene group having 1 to 4 carbon atoms, and R _c is an optionally branched alkylene group having 1 to 4 carbon atoms. , is an optionally branched alkyl group having 1 or more and 8 or less carbon atoms. n represents an integer of 1 or more and 4 or less.)

Note that R1 is preferably an optionally branched alkyl group having 1 to 4 carbon atoms. R2 is preferably a 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.

Examples of the organic solvent represented by formula (2) include 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, and tripropylene glycol ethyl methyl ether. can be mentioned.

From the viewpoint of permeability into the base material on which the non-aqueous ink composition is discharged, leveling property on the base material surface, and drying property, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dipropyl ether, and diethylene glycol are used. 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 Preferred examples include glycol methylpropyl ether, dipropylene glycol dipropyl ether, tripropylene glycol dimethyl ether, and tripropylene glycol ethyl methyl ether.

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 cleaning recovery properties 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 properties on a substrate can be obtained. By containing a glycol ether solvent with a flash point of 70°C or higher and a glycol ether solvent with a flash point of lower than 70°C, it is possible to achieve both high cleaning recovery properties and surface drying properties on the substrate. This results in a non-aqueous ink composition that particularly effectively exhibits the effects of the present invention.

Moreover, it is more preferable to contain 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. It becomes possible to achieve both the storage stability of the non-aqueous ink composition, the high cleaning recovery property, and the surface drying property on the substrate, resulting in a non-aqueous ink composition that 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 organic solvents mentioned above. Specific examples include glycol ether monoalkyl in which one OH group of glycol is substituted with alkyl. Examples of glycol ether monoalkyl solvents include ethylene glycol mono-n-butyl ether, ethylene glycol mono-isobutyl ether, ethylene glycol mono-t-butyl ether, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol monomethyl (or ethyl, propyl , isopropyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl ether, triethylene glycol monomethyl (or ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl) ether, tetraethylene glycol monomethyl Ether, 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 (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 other alkylene glycol monoalkyl ethers.

Moreover, other solvents than the glycol ether solvent may be contained. Specifically, oxazolidinone solvents different from the cyclic amide solvent of formula (4) above, such as 3-methyl-2-oxazolidinone, 3-ethyl-2-oxazolidinone, and N-vinylmethyloxazolidinone, and triethylene glycol butyl ether acetate. , acetate solvents such as 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, etc. -Methoxypropanamide, 3-butoxypropanamide, N,N-dimethyl-3-methoxypropanamide, N,N-dibutyl-3-methoxypropanamide, N,N-dibutyl-3-butoxypropanamide, N,N - An amide solvent different from the alkylamide solvent of the above formula (3) such as dimethyl-3-butoxypropanamide or the cyclic amide solvent of the above formula (4), methyl alcohol, ethyl alcohol, n-propyl alcohol, 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 keto alcohols such as acetone and diacetone alcohol; ethers such as tetrahydrofuran and dioxane ; Oxyethylene or oxypropylene copolymers such as polyethylene glycol and polypropylene glycol; ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-propanediol, isobutylene glycol, triethylene glycol, tripropylene glycol, tetraethylene glycol , 1,3-propanediol, 2-methyl-1,2-propanediol, 2-methyl-1,2-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol , 1,2-pentanediol, 1,2-hexanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,3-butanediol , 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol and other diols; glycerin, trimethylolethane, trimethylolpropane, 1,2,6-hexanetriol and other triols: Tetrahydric alcohols such as mesoerythritol and pentaerythritol, monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-ethylethanolamine, N-butylethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, Examples include alkanolamines such as N-butyldiethanolamine. It is preferable to select a solvent with an appropriate HLB value depending on the resin, dispersant, etc. to be combined.

The content of other organic solvents is not particularly limited, but the lower limit of the content of other organic solvents is preferably in the range of 10% by mass or more, more preferably in the range of 20% by mass or more. , more preferably in a range of 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 and preventing solidification of the non-aqueous ink composition in equipment such as nozzles and tubes, and redissolving the non-aqueous ink composition when solidified, In addition, for the purpose of lowering 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 of further improving the glossiness of the recorded matter. Note that surfactants include those called surface conditioning agents, leveling agents, antifoaming agents, and the like.

Among these, the surfactant preferably contains a surfactant having a siloxane skeleton. Pigment A tends to aggregate in a non-aqueous ink composition and tends to have a large volume average particle diameter. As a result, the glossiness of the resulting recorded matter may be reduced. By containing a surfactant having a siloxane skeleton in the non-aqueous ink composition according to the present embodiment, even if pigment A is contained, the glossiness of the resulting recorded product can be improved. Furthermore, if the non-aqueous ink contains a surfactant having a siloxane skeleton, printed matter will have less bleeding and a recorded matter with improved scratch resistance will be obtained.

As the surfactant having a siloxane skeleton, it is preferable to use polyester-modified silicone or polyether-modified silicone, and specific examples include BYK-313, 315N, 322, 326, 331, 347, 348, BYK-UV3500, 3510. , 3530, 3570 (all manufactured by Bikkemie Japan), etc. 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, nonionic polyoxyalkylene alkyl ethers such as P-208, P-210, P-213, E-202S, E-205S, E-215, K-204, K-220, S-207, S-215 , A-10R, A-13P, NC-203, NC-207 (manufactured by NOF Corporation), Emulgen 106, 108, 707, 709, A-90, A-60 (manufactured by Kao Corporation), Florene G-70, D-90, TG-740W (manufactured by Kyoeisha Chemical Co., Ltd.), Poem J-0081HV (manufactured by Riken Vitamin Co., Ltd.), Adekator NP-620, NP-650, NP-660, NP-675, NP-683, NP-686, ADEKA COL CS-141E, TS-230E (manufactured by ADEKA Co., Ltd.), etc., Solgen 30V, 40, TW-20, TW-80, Neugen CX-100 (Daiichi Kogyo Seiyaku Co., Ltd.) As the fluorine-based surfactant, it is preferable to use a fluorine-modified polymer, such as BYK-340 (manufactured by BYK-Chemie Japan), and as the acetylene glycol-based surfactant, as a specific example, , Surfynol (registered trademark) 82, 104, 465, 485, TG (all manufactured by Air Products Japan), Olfine (registered trademark) STG, E1010 (all manufactured by Nissin Chemical Co., Ltd.). The surfactant is not limited to those mentioned above, and any anionic, cationic, amphoteric, or nonionic surfactant 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 also 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 may be 0.01% by mass or more. It is preferably in a range of 0.05% by mass or more, more preferably in a 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. It is even more preferable that it is 1.5% or less, and even more preferable that it is 1.5% or less. When the content of the surfactant is within the above range, it is possible to provide an ink coating film of printed matter with excellent coating film properties 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, etc., polyhydric carboxylic acids, pH adjusters, bactericides, preservatives, deodorants, and charge control agents. , a wetting agent, and other known additives may be included as optional components. Specific examples of the antioxidant include hindered phenol antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, hydrazine antioxidants, and the like. Specific examples include BHA (2,3-butyl-4-oxyanisole) and BHT (2,6-di-t-butyl-p-cresol). Further, as the ultraviolet absorber, a benzophenone compound or a benzotriazole compound can be used. Further, specific examples of epoxides include epoxy glyceride, epoxy fatty acid monoester, and epoxy hexahydrophthalate. Illustrated. Specific examples of polyhydric carboxylic acids include citric acid and maleic acid.

≪2. Method for producing non-aqueous ink composition≫
The method for producing the 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, resin, etc.) using a paint shaker. At this time, each component may be dispersed using zirconia beads. Further, the obtained non-aqueous ink composition may be adjusted to a desired amount of dissolved oxygen and dissolved nitrogen by degassing treatment, etc., if necessary.

Although the non-aqueous ink composition according to the present embodiment is a non-aqueous ink composition that does not intentionally contain water, 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 be as low as possible. If excessive water is contained, storage stability and dischargeability will be poor, and the risk of solid components and the like will be increased. 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, and 0.3% by mass based on the total amount of the non-aqueous ink composition. It is more preferable that it is the following.

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. Methods for drying organic solvents include, for example, spraying an inert gas (e.g., nitrogen gas) dried in an inert gas atmosphere such as nitrogen for a predetermined period of time, purifying the organic solvent by distillation, and selecting water. Examples include a method in which the organic solvent is allowed to permeate through a semi-permeable membrane that is transparent to the organic solvent, and a method in which water mixed in the organic solvent is selectively adsorbed by a water adsorbent that adsorbs water.

≪3. Recording method using ink composition≫
The recording method according to this embodiment is a recording method in which the above-described non-aqueous ink composition is discharged onto the surface of a base material using an inkjet method. The non-aqueous ink composition of the present invention satisfies the characteristics required of a non-aqueous ink composition ejected by an inkjet method, and also in the recording method according to the present embodiment, the non-aqueous ink composition ejected by an inkjet method can be used. This satisfies the characteristics required of a water-based ink composition. The inkjet method for ejecting ink may be a piezo method using a piezoelectric element or a thermal method using a heating element, and is not particularly limited.

≪4. Method of manufacturing recorded materials≫
A recording method using the above-mentioned ink composition can also be defined as a method for producing a recorded material. The method for producing a recorded matter according to the present embodiment also satisfies the characteristics required of a nonaqueous ink composition discharged by an inkjet method.

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

[Media (recording medium)]
The base material (recording medium) that can be used in the recording method according to this embodiment is not particularly limited, and may be a non-absorbent base material such as a resin base material, metal, or plate glass, such as paper or Various types of base materials can be used, including absorbent base materials such as fabrics, and surface-coated base materials such as base materials provided with a receptive layer.

Among these, since the above-mentioned non-aqueous ink composition is a non-aqueous ink composition that does not contain water, one whose surface is mainly made of resin is preferable. In particular, when the above-mentioned non-aqueous ink composition contains an alkylamide solvent, printing on a medium (recording medium) whose surface is made of resin is less likely to bleed, resulting in clearer printing. Examples of the resin include polyvinyl chloride polymer, acrylic, PET, polycarbonate, PE, and PP. Further, it may be used as a resin base material (so-called resin base material for lamination) on which a film is to be laminated to the recording surface of a recorded object. Particularly preferred is a substrate (recording medium) whose surface is made of a hard or soft polyvinyl chloride polymer. Examples of the base material (recording medium) whose surface is made of a polyvinyl chloride polymer include a polyvinyl chloride base material (film or sheet).

[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. Discharging the above non-aqueous ink composition satisfies the characteristics required of a non-aqueous ink composition discharged by an inkjet method.

[Other layers]
The recorded material 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 scratch resistance and gloss to the recorded matter. Furthermore, a layer with an uneven surface (matte surface) may be formed by containing a filler or changing the film thickness on a pixel-by-pixel basis. Further, 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, etc. may be formed.

≪6. Ink set≫
The ink set according to this embodiment is an ink set that includes at least the above-described non-aqueous ink composition. For example, when the above-mentioned non-aqueous ink composition is an orange ink, by combining it with a conventionally known yellow ink, magenta ink, cyan ink, or black ink, in addition to achieving the effects of the present invention, It becomes possible to expand color reproducibility.

Further, an ink set including the above non-aqueous ink composition and glitter ink such as white ink, metallic ink, pearl ink, etc. may be used. Further, an ink set including the above non-aqueous ink composition, clear ink, pre-coating ink, overprint ink, etc. may also be used.

≪7. Inkjet recording device≫
The above-mentioned non-aqueous ink composition satisfies the characteristics required for a non-aqueous ink composition to be ejected by an inkjet method even if a pigment including a perinone pigment is used as a pigment. By using an inkjet recording device equipped with an ink cartridge (equivalent to a storage container) filled with material, the inkjet method is used to eject the material onto the surface of the base material, which improves the glossiness of the printed surface of the resulting printed material. It becomes possible to satisfy the characteristics required of a non-aqueous ink composition.

A conventionally known inkjet recording device can be used as this inkjet recording device. For example, an inkjet printer such as VersaArt RE-640 manufactured by Roland DG Co., Ltd. can be used.

As an example of the configuration of an inkjet recording device, an on-carriage type, serial printer type inkjet recording device will be described. However, an inkjet recording device that can implement the recording method according to this embodiment has an ink cartridge that is external. The inkjet recording device may be an off-carriage type inkjet recording device in which the inkjet head is fixed to the recording medium, or it may be a line printer type inkjet recording device in which the inkjet head ejects the ink composition onto the recording medium (substrate) without moving. good.

Further, it is preferable that the inkjet recording apparatus includes a heating mechanism and a fixing mechanism for fixing the base material. The organic solvent contained in the non-aqueous ink composition is dried by controlling the substrate surface temperature using a heating mechanism provided in the inkjet recording device and drying the non-aqueous ink composition that has landed on the substrate (recording medium). It becomes possible to volatilize.

Furthermore, the fixing mechanism that fixes the base material makes it possible to dry the non-aqueous ink composition while the base material (recording medium) is fixed, and the way the base material is deflected by heating will prevent heat from being applied. Uniformity can be suppressed. This makes it possible to effectively dry the non-aqueous ink composition that has landed on the base material (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 material. Further, 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 it can volatilize the organic solvent contained in the non-aqueous ink composition, and the lower limit of the surface temperature of the substrate is 20°C or higher. The temperature is preferably 30°C or higher, more preferably 40°C or higher, and even more preferably 40°C or higher. The upper limit of the surface temperature of the base material is preferably 70°C or lower, more preferably 60°C or lower, and even more preferably 50°C or lower.

The fixing mechanism for fixing the base material is not particularly limited, and may be a fixing mechanism that fixes the base material using a predetermined jig, or a fixing mechanism that suctions and adsorbs the base material using negative pressure.

The inkjet head for ejecting 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.

Further, the inkjet recording device includes a plastic tube that connects a container (ink cartridge, bottle, etc.) that stores the above-mentioned non-aqueous ink composition and an inkjet ejection port that ejects the above-mentioned non-aqueous ink composition. The non-aqueous ink composition may be supplied to the inkjet head through the plastic tube and ejected by an inkjet method.

Further, it is preferable that the tube connected to the storage mechanism and the inkjet ejection port is provided with 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 via the valve mechanism, a mechanism is provided that can eliminate nozzle clogging, and the ejection stability of the non-aqueous ink composition can be further improved. can.

Further, as described above, the inkjet recording apparatus according to the present embodiment can print inks of various colors such as yellow, magenta, cyan, and black, light magenta, light cyan, light black, orange, green, red, white, metallic, and pearl. , clear, pre-coating, overprint, and other various inks can be used, and there are no particular restrictions on the order of printing colors or the position or configuration of the head. Furthermore, the inkjet recording apparatus according to the present embodiment may or may not include 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.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these descriptions in any way.

1. Preparation of Non-Aqueous Ink Compositions Non-aqueous ink compositions of Examples and Comparative Examples were prepared using the respective organic solvents, resins, dispersants, and pigments (coloring materials) in proportions as shown in the table below. Specifically, a non-aqueous ink composition was prepared by dispersing it in zirconia beads using a paint shaker until the volume-based cumulative 90% particle diameter D90 became 450 nm or less. The unit is 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 measuring device (particle size analyzer NANOTRACWAVE manufactured by Microtrack Bell Co., Ltd.).

2. Evaluation (discharge stability)
The ejection stability of the non-aqueous ink compositions of Examples, Comparative Examples, and Reference Examples was evaluated. Specifically, an inkjet printer (product name: VersaArt RE-640, manufactured by Roland DG Co., Ltd. is used) is filled with a non-aqueous ink composition, and a recording medium (adhesive polyvinyl chloride film (IMAGin JT5829R: MACtac Co., Ltd.) is filled with a non-aqueous ink composition. Print solid lines and fine lines in continuous printing at a substrate surface temperature of 40°C in bi-directional high-speed printing mode (360 x 720 dpi) on a (manufactured by) manufacturer), and visually observe the presence or absence of missing dots, flight bends, and ink splatters. evaluated (described as "discharge stability" in the table).
Evaluation Criteria A: Fine lines are correctly reproduced.
B: There is a slight deviation in the landing position, but the fine lines are generally reproduced correctly.
C: Fine lines cannot be reproduced due to deviation in the landing position.
A and B are within the usable range.
(Storage stability)
The storage stability of the non-aqueous ink compositions of Examples and Comparative Examples was evaluated. 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 from the viscosity 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 range.

(color development)
The color development properties of the non-aqueous ink compositions of Examples and Comparative Examples were evaluated. Specifically, high-quality printing was performed on a recording medium (adhesive polyvinyl chloride film (IMAGin JT5829R: manufactured by MACtac)) using the above inkjet printer (trade name: VersaArt RE-640, manufactured by Roland DG Co., Ltd.). A solid image was printed in mode (1440 x 720 dpi). The saturation was determined 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. (In the table, it is written as "color development").
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 range.

(Glossiness)
The glossiness of the non-aqueous ink compositions of Examples, Comparative Examples, and Reference Examples was evaluated. Specifically, a printed matter was produced in the same manner as in the color development evaluation above, and the 20° glossiness of the printed matter was measured using a hand-held gloss meter Phopoint IQ-S (manufactured by Konica Minolta). (In the table, it is written as "glossy").
Evaluation Criteria A: 20° gloss is 60 or more B: 20° gloss is 55 or more and less than 60 C: 20° gloss is less than 55 A and B are within the practical usable range.

(Abrasion resistance)
The scratch resistance of the non-aqueous ink compositions of Examples, Comparative Examples, and Reference Examples was evaluated. Specifically, a printed matter was produced in the same manner as in the above color development evaluation and glossiness evaluation, and the printed surface of the printed matter was rubbed with a dry cotton cloth 50 times under a load of 200 g, and the abrasion resistance was visually evaluated.
Evaluation Criteria A: No scratches were observed on the printed surface.
B: Slight rubbing was observed on the printed surface, but it was substantially within an acceptable range.
C: Clear peeling was observed on the printed surface.
A and B are within the practical range.

(Solvent resistance)
The solvent resistance of the non-aqueous ink compositions of Examples, Comparative Examples, and Reference Examples was evaluated. Specifically, in the same manner as the above scratch resistance evaluation, the printed surface of the printed matter was rubbed with a cotton cloth impregnated with a 50% by mass alcohol aqueous solution under a load of 200 g, 50 times, and the scratch resistance was visually evaluated.
Evaluation Criteria A: No scratches were observed on the printed surface.
B: Slight rubbing was observed on the printed surface, but it was substantially within an acceptable range.
C: Clear peeling was observed on the printed surface.
A and B are within the practical range.

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

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

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

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

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

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

In the table, "CB" is carbon black.

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

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

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 "Solvine 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 table above, if the non-aqueous ink composition of the example contains pigment A (perinone pigment) represented by formula (1) and the content of the pigment dispersant is less than the content of the pigment, , it can be seen that the properties required for a non-aqueous ink composition discharged by an inkjet method are satisfied.

On the other hand, the non-aqueous ink composition of the comparative example containing pigment A (perinone pigment) represented by formula (1) and in which the content of the pigment dispersant is greater than or equal to the content of the pigment, The glossiness of the ink composition is reduced, and the scratch resistance and solvent resistance are also reduced, and the properties required for a non-aqueous ink composition to be ejected by an inkjet method are not met.

Note that the non-aqueous ink compositions of Reference Examples 1 to 4 that do not contain pigment A (perinone pigment) represented by formula (1) can be processed by the inkjet method even if the content of the pigment dispersant is higher than the content of the pigment. The properties required for a non-aqueous ink composition discharged by From this, it can be seen that the problem of the present invention that pigments aggregate in non-aqueous ink compositions is unique to non-aqueous ink compositions containing pigment A (perinone pigment) represented by formula (1). was confirmed.

Claims (14)

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 pigment A represented by the following formula (1),
The content of the pigment dispersant is smaller than the content of the pigment,
Non-aqueous ink composition.

(In formula (1), X1 to X12 are each independently hydrogen, a halogen atom, an optionally branched alkyl group having 1 to 5 carbon atoms, and an optionally hydrogen-substituted aromatic hydrocarbon group) , cyano group, nitro group, amino group, -OH, -COOH, -COO-M ⁺ , -SO ₃ H, -SO ₃ ^- M ⁺ , phthalimide group where hydrogen atom may be substituted, phthalimidomethyl group, or a heterocyclic compound, and M ⁺ represents a cation.) The content of the resin is greater than the content of the pigment,
The non-aqueous ink composition according to claim 1. The content of the pigment is 1.0% by mass or more,
The non-aqueous ink composition according to claim 1 or 2. The content of the resin is greater than the content of the pigment dispersant,
The non-aqueous ink composition according to any one of claims 1 to 3. (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 4. 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 5. 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 6. (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 7. 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 8. Discharging the non-aqueous ink composition according to any one of claims 1 to 9 onto the surface of a base material by an inkjet method.
Recording method. Discharging the non-aqueous ink composition according to any one of claims 1 to 9 onto the surface of a base material by an inkjet method.
Method of manufacturing recorded materials. comprising at least the non-aqueous ink composition according to any one of claims 1 to 9.
ink set. A printed layer of the non-aqueous ink composition according to any one of claims 1 to 9 is formed on the surface of a base material.
Recorded material. A storage container filled with the non-aqueous ink composition according to any one of claims 1 to 9 is mounted.
Inkjet recording device.