JP5930246B2 - Non-aqueous ink composition for inkjet recording and inkjet recording method - Google Patents

Description

  The present invention relates to a non-aqueous ink composition for ink jet recording and an ink jet recording method using the same.

  Conventionally, so-called inkjet printing, in which images and characters are printed with minute ink droplets ejected from nozzles of an inkjet recording head, has been mainly used for printing on the surface of a water-absorbing recording medium such as paper. As ink-jet inks used in such ink-jet printing, water-based inks in which a color material such as a water-soluble dye is added to water are widely used. However, inkjet printing has recently been used for printing on a variety of recording medium surfaces in various fields. Therefore, in order to cope with printing on a wide variety of recording medium surfaces, a non-aqueous ink substantially free of water as a solvent has been developed in place of the aqueous ink.

  Examples of such non-aqueous inks include glyme (symmetric glycol diether) such as diethylene glycol diethyl ether, glycol dialkyl ether such as diethylene glycol butyl methyl ether, glycol monoalkyl ether such as diethylene glycol monobutyl ether, and dicarboxylic acid such as dimethyl glutarate. Examples thereof include non-aqueous inks composed of diesters, lactones such as γ-butyrolactone, amide solvents such as N-methyl-2-pyrrolidone, and the like (for example, see Patent Document 1). Such a non-aqueous ink is firmly fixed on the surface of the vinyl chloride resin, and the composition is devised so that images and characters excellent in water resistance, light resistance, friction resistance, etc. can be printed on the surface. .

JP 2009-74034 A

  However, since such a non-aqueous ink is premised on printing on a vinyl chloride resin, it is necessary to limit the content of the protic polar solvent. Then, since the proton donating ability becomes poor, the viscosity becomes close to Newtonian flow. When forming ink droplets in the ink jet recording method (especially when using a high frequency), it is necessary to have an appropriate pseudoplastic flow in order to ensure the ejection stability of the ink. Since there was no appropriate material for imparting pseudoplasticity, it was difficult to ensure good ejection stability.

  Further, conventional non-aqueous inks cannot be said to have sufficient fixability to a recording medium made of a vinyl chloride resin, and the recorded images may not have sufficient abrasion resistance.

  Some embodiments according to the present invention provide a non-aqueous ink composition for ink jet which is excellent in ejection stability or recorded image abrasion resistance by solving at least one of the two problems, and uses the same. Ink jet recording method is provided.

  SUMMARY An advantage of some aspects of the invention is to solve at least a part of the problems described above, and the invention can be implemented as the following aspects or application examples.

（式（１）中、Ｒ¹は、炭素数１〜４のアルキル基を表す。） [Application Example 1]
One aspect of the non-aqueous ink composition for inkjet recording according to the present invention is:
It contains at least a solvent represented by the following general formula (1) and having an HLB value of 10.5 or more and 20.0 or less.

(In formula (1), R ¹ represents an alkyl group having 1 to 4 carbon atoms.)

  According to the non-aqueous ink composition for ink-jet recording of Application Example 1, pseudoplasticity is imparted by containing the solvent represented by the general formula (1), and good ejection stability is obtained. Furthermore, an image or a character firmly fixed on the surface of the recording medium by the interaction between the recording medium containing a vinyl chloride resin such as a polyvinyl chloride sheet and the solvent represented by the general formula (1). Can be recorded.

[Application Example 2]
In the non-aqueous ink composition for inkjet recording of Application Example 1, R ^{1 of the} solvent represented by the general formula (1) may be a methyl group or an n-butyl group.

[Application Example 3]
In the non-aqueous ink composition for ink jet recording of Application Example 1 or Application Example 2, the content of the solvent represented by the general formula (1) may be 10% by mass or more and 90% by mass or less.

[Application Example 4]
In the non-aqueous ink composition for ink jet recording of Application Example 1 or Application Example 2, the content of the solvent represented by the general formula (1) may be 30% by mass or more and 90% by mass or less.

[Application Example 5]
The non-aqueous ink composition for ink jet recording according to any one of Application Examples 1 to 4 may further contain at least one selected from a liquid alkylene glycol compound and a lactone at normal temperature and pressure.

[Application Example 6]
The non-aqueous ink composition for ink jet recording according to any one of Application Example 1 to Application Example 5 may further contain a pigment.

[Application Example 7]
In the non-aqueous ink composition for ink jet recording according to any one of Application Example 1 to Application Example 6, the viscosity at a measurement temperature of 20 ° C. may be 2 mPa · s or more and 15 mPa · s or less.

[Application Example 8]
In the non-aqueous ink composition for ink jet recording according to any one of Application Example 1 to Application Example 7, the surface tension at a measurement temperature of 20 ° C. may be 20 mN / m or more and 50 mN / m or less.

[Application Example 9]
One aspect of the inkjet recording method according to the present invention is:
A droplet of the non-aqueous ink composition for ink jet recording described in any one of Application Example 1 to Application Example 8 is ejected, and the droplet is attached to the surface of a recording medium containing a vinyl chloride resin to form an image. It is characterized by recording.

  According to the ink jet recording method of Application Example 9, since the non-aqueous ink composition for ink jet recording is used, good ejection stability from the ink jet head can be secured, and the solvent represented by the general formula (1) By interacting with the vinyl chloride resin in the recording medium, it is possible to firmly fix the image and characters on the surface of the recording medium.

  Hereinafter, preferred embodiments of the present invention will be described in detail. The embodiment described below describes an example of the present invention. In addition, the present invention is not limited to the following embodiments, and includes various modifications that are implemented within a range that does not change the gist of the present invention.

1. Non-aqueous ink composition for ink-jet recording A non-aqueous ink composition for ink-jet recording according to an embodiment of the present invention (hereinafter, also simply referred to as “non-aqueous ink composition”) is a specific solvent for imparting pseudoplasticity. At least. In the present invention, the term “non-aqueous ink composition” means that water is not intentionally added when the ink composition is produced, and a trace amount that inevitably mixes the ink composition during production or storage. It may also contain water.

  Hereinafter, each component used for this Embodiment is demonstrated in detail.

1.1. Solvent The non-aqueous ink composition according to the present embodiment contains at least a solvent represented by the following general formula (1).

As a result of intensive studies, it has been found that in formula (1), R ¹ is preferably an alkyl group having 1 to 4 carbon atoms. The “C1-C4 alkyl group” may be a linear or branched alkyl group such as a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, It can be an iso-butyl group, a sec-butyl group, or a tert-butyl group. The solvent represented by the formula (1) in which R ¹ is an alkyl group having 1 to 4 carbon atoms can impart appropriate pseudoplasticity to the non-aqueous ink composition, thereby ensuring good ejection stability of the ink. be able to. In addition, since the solvent represented by the formula (1) in which R ¹ is an alkyl group having 1 to 4 carbon atoms interacts with the vinyl chloride resin, the ink is strongly applied to the surface of the recording medium containing the vinyl chloride resin. It can be fixed.

The HLB value of the solvent represented by the formula (1) is 10.5 or more and 20.0 or less, preferably 12.0 or more and 18.5 or less. When the HLB value of the solvent represented by the formula (1) is within the above range, it is more preferable from the viewpoint of imparting appropriate pseudoplasticity to the ink and interaction with the vinyl chloride resin. In addition, the HLB value in this specification is the following formula (2) from the ratio of the nonpolar value (I) and the organic value (O) in the organic conceptual diagram (hereinafter also simply referred to as “I / O value”). Is a value calculated by
HLB value = (Nonpolar value (I) / Organic value (O)) × 10 (2)
Specifically, I / O values are written by Atsushi Fujita, “Systematic Organic Qualitative Analysis Mixture”, Kazama Shobo, 1974; Norihiko Kuroki, “Dyeing Theoretical Chemistry”, Sakai Shoten, 1966; Hiroo Inoue , “Organic Compound Separation Method”, Suikabo, 1990.

  The content of the solvent represented by the formula (1) in the non-aqueous ink composition according to this embodiment is preferably 10% by mass to 90% by mass, more preferably 30% by mass to 90% by mass. is there. When the content of the solvent represented by the formula (1) is 10% by mass or more, moderate pseudoplasticity is imparted to the non-aqueous ink composition, and ink ejection stability can be ensured. Further, when the content of the solvent represented by the formula (1) is 30% by mass or more, it is possible to further improve the abrasion resistance of an image recorded by the interaction with the vinyl chloride resin.

1.2. Other additives To the non-aqueous ink composition according to the present embodiment, an organic solvent other than the solvent represented by the formula (1), a surfactant, a pigment, a dispersant, and the like are added as necessary. Also good.

1.2.1. Other Organic Solvents The non-aqueous ink composition according to the present embodiment is at least one selected from a liquid alkylene glycol compound and a lactone at room temperature and normal pressure from the viewpoint of firmly fixing the ink to the vinyl chloride resin. It is preferable to contain a seed, and it is more preferable to contain an alkylene glycol compound.

  The alkylene glycol compound is preferably an ethylene glycol compound or a propylene glycol compound as described in International Publication No. 2002/055619 pamphlet.

  Preferred ethylene glycol compounds include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, or polyethylene glycol monoethers or diethers, with diethylene glycol compounds being preferred. Preferred propylene glycol compounds include propylene glycol, dipropylene glycol, tripropylene glycol, or polypropylene glycol monoether or diether, preferably dipropylene glycol.

  As the diethylene glycol compound, for example, a diethylene glycol compound represented by the following general formula (3) can be used.

In formula (3), R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an R ⁴ CO group. R ⁴ is an alkyl group having 1 to 4 carbon atoms. “1 to 4 carbon atoms
The “alkyl group of” can be a linear or branched alkyl group, for example, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, or It can be a tert-butyl group. Specific examples of the diethylene glycol compound represented by the formula (3) include diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono n-butyl ether, diethylene glycol di n-butyl ether, Examples include diethylene glycol butyl methyl ether, diethylene glycol monoethyl ether acetate, and diethylene glycol mono n-butyl ether acetate.

  As the dipropylene glycol compound, for example, a dipropylene glycol compound represented by the following general formula (4) can be used.

In formula (4), R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an R ⁷ CO group. R ⁷ is an alkyl group having 1 to 4 carbon atoms. The “C1-C4 alkyl group” may be a linear or branched alkyl group such as a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, It can be a sec-butyl group or a tert-butyl group. Examples of the dipropylene glycol compound represented by the formula (4) include dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and the like.

  The lactone is preferably a lactone having 6 or less carbon atoms, more preferably β-propiolactone, β-butyrolactone, γ-butyrolactone, γ-valerolactone, or ε-caprolactone.

  The diethylene glycol compound, the dipropylene glycol compound, and the lactone that can be used in the non-aqueous ink composition according to the present embodiment preferably have a boiling point of 150 ° C. or higher, more preferably 180 ° C., under normal pressure. That's it.

  Further, the diethylene glycol compound and the dipropylene glycol compound that can be used in the non-aqueous ink composition according to the present embodiment have a vapor pressure at 20 ° C. of preferably 1 hPa or less, more preferably 0.7 hPa or less. It is.

  By using a diethylene glycol compound and a dipropylene glycol compound that satisfy the high boiling point and low vapor pressure conditions as described above, the burden of installing a local exhaust facility or exhaust gas treatment facility is reduced, and the work environment can be improved. It is also possible to reduce the environmental load on the surrounding environment.

  In the non-aqueous ink composition according to the present embodiment, it is preferable to contain the diethylene glycol compound, and the content can be appropriately selected depending on the printing characteristics, but with respect to the total mass of the non-aqueous ink composition. It is preferable that it is 20 mass% or more and 80 mass% or less.

In addition to the diethylene glycol compound, dipropylene glycol compound, lactone or a mixture thereof, the non-aqueous ink composition according to the present embodiment is liquid at normal temperature and pressure, and is represented by the following general formula (5). A polyethylene glycol monoether compound may be contained.

In formula (5), R ⁸ and R ⁹ are each independently an alkyl group having 1 to 6 carbon atoms (preferably an alkyl group having 1 to 4 carbon atoms). n is an integer of 3-6. The “C 1-6 alkyl group” may be a linear or branched alkyl group. For example, in addition to the “C 1-4 alkyl group”, a linear or branched alkyl group may be used. It can be a pentyl group or a hexyl group.

  The polyethylene glycol monoether compound that can be used in the non-aqueous ink composition according to the present embodiment has a boiling point of 200 ° C. or higher, more preferably 250 ° C. or higher, under normal pressure. The flash point is preferably 100 ° C. or higher, more preferably 130 ° C. or higher. By using such a polyethylene glycol monoether compound, volatilization suppression can be imparted to the non-aqueous ink composition. For example, by suppressing the volatilization of the non-aqueous ink composition in the tube that transports the non-aqueous ink composition from the ink cartridge to the inkjet recording head, it is possible to prevent or reduce the accumulation of solids in the tube. it can.

  As a preferable polyethylene glycol monoether compound, for example, a triethylene glycol monoether compound (for example, triethylene glycol monomethyl ether or triethylene glycol monobutyl ether) or n in the general formula (5) is 4-6. A mixture of polyethylene glycol monoether compounds (particularly, polyethylene glycol monomethyl ether), for example, a mixture of tetraethylene glycol monomethyl ether, pentaethylene glycol monomethyl ether, and hexaethylene glycol monomethyl ether can be mentioned.

  Moreover, the non-aqueous ink composition according to the present embodiment may further contain an organic solvent exemplified below in addition to the organic solvent exemplified above.

  Other organic solvents are preferably polar organic solvents, such as alcohols (eg, methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, fluorinated alcohol), ketones (eg, acetone, methyl ethyl ketone, cyclohexanone, etc.) Carboxylic acid esters (eg, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, etc.), ethers (eg, diethyl ether, dipropyl ether, tetrahydrofuran, dioxane, etc.), etc. It is done.

  When the non-aqueous ink composition according to the present embodiment includes at least one of the diethylene glycol compound, the dipropylene glycol compound, and the lactone and does not include the polyethylene glycol monoether compound, the diethylene glycol The total amount of the compound, the dipropylene glycol compound, and the lactone preferably accounts for 75% by mass or more of the total organic solvent component.

Further, when the non-aqueous ink composition according to the present embodiment includes the polyethylene glycol monoether compound in addition to the diethylene glycol compound, the dipropylene glycol compound, and the lactone, the diethylene glycol compound, the diethylene glycol compound, The total amount of the propylene glycol compound, the lactone, and the polyethylene glycol monoether compound preferably occupies 80% by mass or more of the total organic solvent component.

1.2.2. Surfactant In addition to the organic solvent, the non-aqueous ink composition according to the present embodiment includes a silicon-based surfactant and a fluorine-based interface from the viewpoint of reducing surface tension and improving wettability with a recording medium. You may add the activator or the polyoxyethylene derivative which is a nonionic surfactant.

  As the silicon surfactant, it is preferable to use polyester-modified silicon or polyether-modified silicon. Specific examples include BYK-347, 348, BYK-UV3500, 3510, 3530, 3570 (all manufactured by Big Chemie Japan).

  As the fluorine-based surfactant, a fluorine-modified polymer is preferably used, and specific examples thereof include BYK-340 (manufactured by BYK Japan).

  As the polyoxyethylene derivative, it is preferable to use an acetylene glycol surfactant. Specific examples include Surfinol 82, 104, 465, 485, TG (all manufactured by Air Products Japan), Olphine STG, E1010 (all manufactured by Nissin Chemical Co., Ltd.), Nissan Nonion A-10R, A-13R. (All manufactured by NOF Corporation), Floren TG-740W, D-90 (manufactured by Kyoeisha Chemical Co., Ltd.), Neugen CX-100 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and the like.

  The content of the surfactant in the non-aqueous ink composition according to this embodiment is preferably 0.05% by mass or more and 3% by mass or less, more preferably 0.5% by mass or more and 2% by mass or less.

1.2.3. Pigment and Dispersant In the non-aqueous ink composition according to the present embodiment, a pigment such as a colored inorganic pigment or a colored organic pigment usually used in a conventional non-aqueous ink composition can be used as a coloring material. . These pigments may be used alone or in combination of two or more.

  Examples of the pigment include azo pigments such as azo lake, insoluble azo pigment, condensed azo pigment, chelate azo pigment; phthalocyanine pigment, perylene and perylene pigment, anthraquinone pigment, quinacridone pigment, dioxazine pigment, thioindigo pigment, isoindolinone pigment, quinophthalone Polycyclic pigments such as pigments; dye lakes such as basic dye type lakes and acid dye type lakes; organic pigments such as nitro pigments, nitroso pigments, aniline black, daylight fluorescent pigments; inorganic pigments such as carbon black It is done. The average primary particle size of the pigment particles is not particularly limited, but is preferably 50 nm or more and 500 nm or less.

Examples of the pigment when the non-aqueous ink composition according to this embodiment is magenta or red ink include C.I. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment red 15, C.I. I. Pigment red 16, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 139, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 170, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment Red 194
, C.I. I. Pigment red 209, C.I. I. Pigment red 222, C.I. I. And CI Pigment Red 224.

  Examples of the pigment when the non-aqueous ink composition according to this embodiment is an orange or yellow ink include C.I. I. Pigment orange 31, C.I. I. Pigment orange 43, C.I. I. Pigment orange 64, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 150, C.I. I. And CI Pigment Yellow 180.

  Examples of the pigment when the non-aqueous ink composition according to this embodiment is a green or cyan ink include C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 16, C.I. I. Pigment blue 60, C.I. I. Pigment green 7, C.I. I. And CI Pigment Green 36.

  Examples of the pigment when the non-aqueous ink composition according to this embodiment is a black ink include carbon black.

  Examples of the pigment when the non-aqueous ink composition according to this embodiment is a white ink include Pigment White 6, 18, 21 and the like.

  The content of the pigment in the non-aqueous ink composition according to this embodiment can be appropriately selected depending on the application and printing characteristics, but is preferably 0.5% by mass or more and 25% by mass or less, more preferably 0.8%. 5 mass% or more and 15 mass% or less, Especially preferably, they are 1 mass% or more and 10 mass% or less.

  In the non-aqueous ink composition according to this embodiment, any dispersant used in a normal non-aqueous ink composition can be used from the viewpoint of improving the dispersion stability of the pigment. As the dispersant, it is preferable to use a dispersant that works effectively when the solubility parameter of the organic solvent is 8 to 11. Specific examples of such a dispersant include polyester polymers such as Hinoact KF1-M, T-6000, T-7000, T-8000, T-8350P, and T-8000E (all manufactured by Takefu Fine Chemical Co., Ltd.). Compound, Solsperse 20000, 24000, 32000, 32500, 33500, 34000, 35200, 37500 (all manufactured by LUBRIZOL), Disperbyk-161, 162, 163, 164, 166, 180, 190, 191, 192 (all are Big Chemie Japan) ), Floren DOPA-17, 22, 33, G-700 (all manufactured by Kyoeisha Chemical Co., Ltd.), Ajisper PB821, PB711 (all manufactured by Ajinomoto Co., Inc.), LP4010, LP4050, LP4055, P LYMER400,401,402,403,450,451,453 (both EFKA Chemicals Co., Ltd.), and the like.

  In the non-aqueous ink composition according to the present embodiment, the content of the dispersant can be appropriately selected depending on the pigment to be dispersed, but the content of the pigment in the non-aqueous ink composition is 100 parts by mass. And preferably 5 parts by mass or more and 200 parts by mass or less, more preferably 30 parts by mass or more and 120 parts by mass or less.

1.2.4. Other Additives Other additives contained in a normal non-aqueous ink composition may be further added to the non-aqueous ink composition according to the present embodiment. Examples of other additives include stabilizers such as antioxidants and ultraviolet absorbers, and binder resins.

  Examples of the antioxidant include BHA (2,3-butyl-4-oxyanisole), BHT (2,6-di-t-butyl-p-cresol) and the like. The content of the antioxidant in the non-aqueous ink composition according to this embodiment is preferably 0.01% by mass or more and 3% by mass or less.

  Examples of the ultraviolet absorber include benzophenone compounds and benzotriazole compounds. The content of the ultraviolet absorber in the non-aqueous ink composition according to this embodiment is preferably 0.01% by mass or more and 0.5% by mass or less.

  In the non-aqueous ink composition according to this embodiment, a binder resin may be added for the purpose of adjusting the viscosity of the ink. Examples of the binder resin include acrylic resins, styrene acrylic resins, rosin modified resins, phenol resins, terpene resins, polyester resins, polyamide resins, epoxy resins, vinyl chloride vinyl acetate copolymer resins, cellulose acetate butyrate, and the like. Resin, vinyltoluene-α-methylstyrene copolymer resin, and the like. These binder resins may be used alone or in combination of two or more. The binder resin can further improve the fixability of the ink to the vinyl chloride resin depending on the amount of the binder resin added.

1.2.5. Method for Producing Non-Aqueous Ink Composition The non-aqueous ink composition according to the present embodiment can be produced by a known conventional method. When using a pigment as a coloring material, first, after a pigment, a dispersant, and a diethylene glycol compound (part) are mixed, a pigment dispersion is prepared by a ball mill, a bead mill, an ultrasonic wave, a jet mill, or the like. Adjust to have ink characteristics. Subsequently, the solvent represented by the formula (1), the diethylene glycol compound (remaining amount), and other additives (for example, a surfactant or a binder resin) are added with stirring to obtain a non-aqueous ink composition. it can.

1.2.6. Physical Properties The non-aqueous ink composition according to this embodiment has a surface tension at 20 ° C. of 20 mN / m or more and 50 mN / m from the viewpoint of the balance between print quality and reliability as an ink composition for inkjet. Preferably, it is 25 mN / m or more and 40 mN / m or less. The surface tension is measured by using an automatic surface tension meter CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.) by confirming the surface tension when the platinum plate is wetted with ink in an environment of 20 ° C. be able to.

  From the same viewpoint, the viscosity at 20 ° C. of the non-aqueous ink composition according to the present embodiment is preferably 2 mPa · s to 15 mPa · s, and preferably 2 mPa · s to 10 mPa · s. Is more preferable. The viscosity is measured by using a viscoelasticity tester MCR-300 (manufactured by Pysica), increasing the Shear Rate to 10 to 1000 in an environment of 20 ° C., and reading the viscosity at Shear Rate 200. Can be measured.

2. Inkjet recording method The inkjet recording method according to the present embodiment records an image by ejecting droplets of the non-aqueous ink composition described above and attaching the droplets to the surface of a recording medium containing a vinyl chloride resin. It is characterized by doing. The non-aqueous ink composition described above contains the solvent represented by the general formula (1), and the solvent interacts with the vinyl chloride resin. Therefore, the ink jet recording method according to the present embodiment records an image on a recording medium by recording the image by attaching droplets of the non-aqueous ink composition described above to the surface of the recording medium containing the vinyl chloride resin. It is excellent in that it is firmly fixed.

  The recording medium in the ink jet recording method according to the present embodiment is not particularly limited as long as it contains a vinyl chloride resin. Examples of the recording medium containing a vinyl chloride resin include a hard or soft vinyl chloride film or sheet. The non-aqueous ink composition described above makes it possible to record an image on an untreated surface of a vinyl chloride resin base material, and an expensive recording medium such as a recording medium having a conventional receiving layer can be used. Needless to say, the present invention can be applied even to a substrate surface-treated with an ink receiving layer, although it has an excellent effect of making it unnecessary.

  The ink jet recording apparatus used in the ink jet recording method according to the present embodiment is not particularly limited, but a drop-on-demand ink jet recording apparatus is preferable. The drop-on-demand ink jet recording apparatus employs a piezoelectric element recording method in which recording is performed using a piezoelectric element disposed in a recording head, and heat generated by a heater of a heating resistance element disposed in the recording head. There are methods that employ a thermal jet recording method in which recording is performed using energy, and any recording method can be employed. Further, since the non-aqueous ink composition according to the present embodiment has an advantage that it is inactive with respect to the discharge nozzle surface subjected to the ink repellent treatment, for example, for inkjet recording having the discharge nozzle surface subjected to the ink repellent treatment. It can be advantageously used in an ink jet recording method for discharging from a head.

3. Examples Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited to these examples.

なお、得られた溶剤Ａの、有機概念図におけるＩ／Ｏ値から上記式（２）により算出されたＨＬＢ値は、１８．３であった。 3.1. Synthesis of solvent 3.1.1. Solvent A
In a 300 ml separable flask equipped with a stirrer, a thermocouple, and a nitrogen gas inlet tube, 19.828 g of N, N-dimethylacrylamide and 6.408 g of methanol were added and stirred while introducing nitrogen gas. Next, 0.338 g of sodium t-butoxide was added and reacted at 35 ° C. for 4 hours. After completion of heating, 150 mg of phosphoric acid was added to make the solution uniform, and the mixture was allowed to stand for 3 hours. The solution was filtered to remove precipitates, and unreacted substances were removed with an evaporator. Thus, a solvent A represented by the following formula (6) was obtained.

In addition, the HLB value calculated by the said Formula (2) from the I / O value in an organic conceptual diagram of the obtained solvent A was 18.3.

なお、得られた溶剤Ｂの、有機概念図におけるＩ／Ｏ値から上記式（２）により算出されたＨＬＢ値は、１２．２であった。 3.1.2. Solvent B
N, N-dimethylacrylamide (19.828 g) and 1-butanol (14.824 g) were placed in a 300 ml separable flask equipped with a stirrer, a thermocouple, and a nitrogen gas inlet tube, and stirred while introducing nitrogen gas. Next, 0.338 g of sodium t-butoxide was added and reacted at 35 ° C. for 4 hours. After completion of heating, 150 mg of phosphoric acid was added to make the solution uniform, and the mixture was allowed to stand for 3 hours. The solution was filtered to remove precipitates, and unreacted substances were removed with an evaporator. In this way, a solvent B represented by the following formula (7) was obtained.

In addition, the HLB value calculated by the said Formula (2) from the I / O value in an organic conceptual diagram of the obtained solvent B was 12.2.

3.2. Preparation of non-aqueous ink composition Into a container, an amount of a solvent corresponding to the concentration shown in Tables 1 to 3 was charged for each ink, and mixed and stirred for 30 minutes using a magnetic stirrer to obtain a mixed solvent. .
Part of the obtained mixed solvent was separated, and Solsperse 37500 (trade name, manufactured by LUBRIZOL) and C.I. I. A predetermined amount of Pigment Black 7 (trade name “CARBON BLACK” manufactured by Mitsubishi Chemical Corporation) was added, and the mixture was pulverized using a homogenizer. Then, the pigment dispersion liquid was obtained by performing a dispersion process with the bead mill filled with the zirconia bead of diameter 0.3mm.
To the obtained pigment dispersion, the remainder of the mixed solvent and BYK-340 (made by Big Chemie Japan Co., Ltd., fluorinated surfactant) were added and further mixed and stirred for 1 hour, and then a 5 μm PTFE membrane filter was added. By using and filtering, the black ink composition of Tables 1-3 was obtained. In addition, the numerical value in a table | surface represents the mass%.

The materials used in the table are as follows.
・ C. I. Pigment Black 7 (Mitsubishi Chemical Corporation, trade name “Carbon Black”, black pigment)
・ Solsperse 37500 (trade name, manufactured by LUBRIZOL, dispersant)
・ Γ-Butyrolactone (trade name, manufactured by Kanto Chemical Co., Inc., solvent)
・ N-methylpyrrolidone (trade name, manufactured by Kanto Chemical Co., Inc., solvent)
・ 2-Pyrrolidone (trade name, manufactured by Kanto Chemical Co., Inc., solvent)
・ Dimethyl sulfoxide (trade name, manufactured by Kanto Chemical Co., Inc., solvent)
・ Dimethyl succinate (trade name, manufactured by Kanto Chemical Co., Inc., solvent)
・ Diethyl succinate (trade name, manufactured by Kanto Chemical Co., Inc., solvent)
・ Dimethyl glutarate (trade name, manufactured by Kanto Chemical Co., Ltd., solvent)
・ Tetraethylene glycol dimethyl ether (trade name, manufactured by Nippon Emulsifier Co., Ltd., solvent) ・ Triethylene glycol dimethyl ether (trade name, manufactured by Japan Emulsifier Co., Ltd., solvent)
・ Diethylene glycol diethyl ether (trade name, manufactured by Nippon Emulsifier Co., Ltd., solvent)
・ Diethylene glycol butyl methyl ether (trade name “Hisolv BDM”, manufactured by Toho Chemical Co., Ltd., solvent)
-BYK-340 (trade name, manufactured by BYK Japan, fluorinated surfactant)

3.3. Evaluation test 3.3.1. Friction fastness test Using a printer “SP-300V” manufactured by J Roland DG, each ink composition obtained in “3.2. Preparation of Non-Aqueous Ink Composition” was treated with a glossy polyvinyl chloride sheet (Roland DG). And “SV-G-1270G”), and printing was performed under the condition of Duty 100%. Then, the sample for evaluation was obtained by making it dry at normal temperature for 1 day.
Next, in accordance with Japanese Industrial Standard “JIS L 0849”, a dry test was performed on an evaluation sample using an I-type testing machine. Then, the OD value of the sample for evaluation is spectrolino (
(Measured by Gretag Macbeth). The evaluation criteria are as follows. The evaluation results are also shown in Tables 1 to 3.
7: OD value is less than 0.15 6: OD value is 0.15 or more and less than 0.20 5: OD value is 0.20 or more and less than 0.25 4: OD value is 0.25 or more and less than 0.30 3: OD value is 0.30 or more and less than 0.35 2: OD value is 0.35 or more and less than 0.40 1: OD value is 0.40 or more

3.3.2. Surface dryness test Using a printer “SP-300V” manufactured by J Roland DG, each ink composition obtained in “3.2. Preparation of Non-Water-Based Ink Composition” was used as a glossy polyvinyl chloride sheet (Roland DG). (“SV-G-1270G”) manufactured under the condition of 100% duty, and then dried for 5 minutes. Next, the scratch marks on the glossy surface after the glossy polyvinyl chloride sheet was wound up using a winder were observed. The scratch marks were observed by measuring the surface roughness with a shape measurement laser microscope (manufactured by Keyence Corporation, “VK-8700 Generation II”) to calculate the ratio of the area with the scratch marks. The evaluation criteria are as follows. The evaluation results are also shown in Tables 1 to 3.
5: Scratch area is less than 10% 4: Scratch area is 10% or more and less than 20% 3: Scratch area is 20% or more and less than 30% 2: Scratch area is 30% or more and less than 40% 1: Scratch area 40% or more

3.3.3. Discharge amount test Each ink composition obtained in “3.2. Preparation of non-aqueous ink composition” was ejected from an ink jet recording head mounted on a printer “SP-300V” manufactured by J Roland DG. The amount of discharge was determined. The ejection amount is measured by a reduction method that measures a reduction in the amount of ink supplied to the ink jet recording head. The evaluation result is a weight loss method when the ink composition is ejected by setting a reference driving voltage and waveform capable of ejecting 7 ng of the ink composition of Example 3 at a frequency of 14.4 kHz in a temperature 25 ° C./humidity 40% environment. It is the result calculated by. The evaluation results are also shown in Tables 1 to 3.

  When fixing a pigment on the surface of a recording medium using a pigment as a coloring material, it is better to record an image with large droplets than to record an image with a plurality of small droplets arranged side by side. Color development (OD value) tends to be high. That is, it can be said that securing a larger ink discharge amount is advantageous in terms of enhancing the color developability.

3.3.4. High frequency compatibility test Using the head mounted on the printer “SP-300V” manufactured by J Roland DG, the head drive frequency was changed, and the “droplet shape” and “ It was evaluated whether discharge was performed without “flight bend” or whether these evaluation items were guaranteed even during continuous discharge (continuous discharge stability), and the highest frequency satisfying all the evaluation items was determined. The evaluation results are also shown in Tables 1 to 3.

3.3.5. Evaluation Results According to Examples 1 and 2, since moderate pseudoplasticity was imparted to the ink by containing the solvent A or the solvent B, good results were obtained in the evaluation test of the discharge amount and high frequency compatibility. It was found that stable discharge stability can be secured. In addition, good results were obtained in the evaluation test of friction fastness, and it was found that the ink was firmly fixed on the glossy polyvinyl chloride sheet to improve the abrasion resistance. Furthermore, it was found that the surface drying property of the ink was excellent.

  According to Examples 3 to 11, it was found that when an ink containing a solvent other than the solvent A and the solvent B was used, it was significantly inferior to Examples 1 to 2 particularly in the high frequency compatibility evaluation test. Also, it was found that the frictional fastness evaluation test was significantly inferior to Examples 1 and 2.

  The results of Examples 12 to 22 were the same as those of Examples 1 to 11 described above.

  According to Examples 23 and 24, an appropriate pseudoplastic property was imparted to the ink by containing the solvent A or the solvent B without containing the pigment, and therefore, good results were obtained in the evaluation test of the discharge amount and the high frequency compatibility. It was found that good ejection stability can be secured. From this result, it was suggested that the material contributing to the ejection stability is the solvent A or the solvent B. Furthermore, it was found that the surface drying property of the ink was excellent.

  The present invention is not limited to the above-described embodiments, and various modifications can be made. For example, the present invention includes substantially the same configuration (for example, a configuration having the same function, method, and result, or a configuration having the same purpose and effect) as the configuration described in the embodiment. In addition, the invention includes a configuration in which a non-essential part of the configuration described in the embodiment is replaced. In addition, the present invention includes a configuration that achieves the same effect as the configuration described in the embodiment or a configuration that can achieve the same object. In addition, the invention includes a configuration in which a known technique is added to the configuration described in the embodiment.

Claims (11)

A droplet of a non-aqueous ink composition for ink jet recording containing at least a solvent represented by the following general formula (1) is ejected, the frequency of ejecting the droplet is 45 kHz or more and 50 kHz or less , and the droplet is recorded on a recording medium. An ink jet recording method in which an image is recorded by adhering to the surface of the ink.

(In formula (1), R ¹ represents an alkyl group having 1 to 4 carbon atoms.) In claim 1,
An inkjet recording method, wherein R ^{1 of the} solvent represented by the general formula (1) contained in the non-aqueous ink composition for inkjet recording is a methyl group. In claim 1 or claim 2,
The inkjet recording method whose content of the solvent shown by the said General formula (1) in the said non-aqueous ink composition for inkjet recordings is 10 mass% or more and 90 mass% or less. In claim 1 or claim 2,
The inkjet recording method whose content of the solvent shown by the said General formula (1) in the said non-aqueous ink composition for inkjet recording is 38 mass% or less. In any one of Claims 1 thru | or 4,
The inkjet recording method, wherein the non-aqueous ink composition for inkjet recording further contains at least one selected from an alkylene glycol compound and a lactone that are liquid at normal temperature and pressure. In any one of Claims 1 thru | or 5,
The inkjet recording method, wherein the non-aqueous ink composition for inkjet recording further contains a pigment. In any one of Claims 1 thru | or 6,
The ink jet recording method, wherein the viscosity of the non-aqueous ink composition for ink jet recording at a measurement temperature of 20 ° C. is 2 mPa · s or more and 15 mPa · s or less. In any one of Claims 1 thru | or 7,
The ink jet recording method wherein the non-aqueous ink composition for ink jet recording has a surface tension at a measurement temperature of 20 ° C. of 20 mN / m or more and 50 mN / m or less. In any one of Claims 1 thru | or 8,
The ink jet recording method, wherein the non-aqueous ink composition for ink jet recording contains 60% by mass or more of a diethylene glycol compound. In any one of Claims 1 thru | or 9,
An ink jet recording method, wherein the recording medium is a recording medium containing a vinyl chloride resin.   The non-aqueous ink composition for inkjet recording used for the inkjet recording method as described in any one of Claims 1 thru | or 10.