JP2007230021A - RECORDING INK, RECORDING MEDIUM SET, INK CARTRIDGE, AND INKJET RECORDING METHOD - Google Patents

Abstract

[PROBLEMS] To print on plain paper and inkjet exclusive paper, and further to a non-porous substrate having a low water absorption capability such as a plastic sheet such as a polyester sheet, a plastic film laminated paper, a plastic surface sheet, or glass or metal. A water-based ink and medium set that can be printed on any medium that can be printed and a printing method are also provided.
A recording ink containing at least a colorant, a water-dispersible resin, a wetting agent, a surfactant, and water, and a recording medium (media) for printing using the ink. The recording ink is suitable for direct recording on a non-porous substrate as a recording medium (medium), and the colorant and water-dispersible resin in the recording ink are used. A set of inkjet ink and media, wherein the total content is 10 to 40% by mass in terms of solid content, and the amount of resin in the total solid content is 60% by mass or more.
[Selection] Figure 1

Description

    The present invention relates to a plastic film sheet such as a polyester film as a non-porous substrate, a plastic film laminated paper, a plastic such as a resin processed paper coated with or impregnated with a plastic material and the paper surface is covered with a plastic material. The present invention relates to a film sheet having a porous surface (referred to as “plastic surface sheet” in the present invention), a water-based ink for printing on a medium having a low water absorption capability such as glass or metal, and a set of media (non-porous recording medium). In addition, it is possible to print on ordinary ink jet recording media such as plain paper, ink jet exclusive paper, gloss paper, or offset coated paper. The present invention also relates to an ink jet recording method for printing on such a non-porous substrate.

Inkjet recording apparatuses are known as image forming apparatuses such as printers, facsimiles, and copying machines. An ink jet recording apparatus performs recording by ejecting ink from a recording head onto a recording medium such as paper. Since the image forming process is simple, the apparatus is easy to simplify, and since it does not go through a heating process, it is energy saving and environmentally friendly. High-definition images can be recorded at high speed, running costs are low, noise is low, and it is easy to record color images using multicolor inks. Yes.
Ink used for such ink jet recording is mainly composed of water, and water-based inks containing a colorant, a wetting agent such as glycerin, a surfactant, and other additives are generally used for home and office applications. Has been used.

In general, as recording media, special paper such as ink-jet paper having a surface coated with a water-absorbing material such as silica or high-quality paper is used.
Patent Document 1 (Japanese Patent Laid-Open No. 2003-226827) discloses an ink having a viscosity of 5 mPa · s or more containing a fluorosurfactant and a polymer emulsion in which a polymer fine particle contains a water-insoluble or hardly water-soluble colorant. Are listed. However, there is no mention of printing on a non-porous medium such as a plastic film.
On the other hand, when printing on a non-water-absorbing medium such as a polyester sheet, an ultraviolet curable ink is generally used because normal ink is inferior in fixability and drying property (Patent Document 2: Japanese Patent Laid-Open No. 2000-1990). 117960 publication).
However, due to the necessity of strong ultraviolet light and the storage stability of the ink, the apparatus becomes larger and is not generally used as a printer.
On the other hand, there is also a method for improving drying property and fixing property with oil-based ink. In this case, since the solvent is an organic solvent, it is not generally used in a place where an organic solvent is hated such as an office.

  In the previous patent, we proposed an aqueous ink with many resin components and a high solid content concentration for improving the image quality on plain paper (Japanese Patent Application No. 2005-241860 of Patent Document 3).

However, there is no mention of the printability of a non-porous substrate having a low water absorption capacity such as an ink film.
As a water-based ink for printing on a polyolefin film, there is, for example, Patent Document 4 (Japanese Patent Application Laid-Open No. 4-139271). However, there is no description that it can be used for inkjet ink.
Patent document 5 (Unexamined-Japanese-Patent No. 2005-15672) discloses the technique about the non-aqueous inkjet ink for polyvinyl chloride resin sheets. This is a non-aqueous ink and is not suitable for the office in terms of environment such as odor.
As an inkjet ink that is printed on a non-porous substrate such as a vinyl medium, there is one described in Japanese Patent Application Laid-Open No. 2005-220352. As far as the examples are concerned, the total solid content is 6% by weight and the wetting agent is 21%.
Ink with such a low solid content, a large amount of wetting agent, and a relatively low viscosity has a large amount of ink adhering per unit area. Easy to happen.
On the other hand, Japanese Patent Application Laid-Open No. 2000-44858 of Patent Document 7 discloses an ink-jet ink for printing on vinyl, which is dried at 70 ° C. in an example. Further, in the examples, since the amount of the wetting agent in the ink is large and the solid content is as small as about 10% or less, it is estimated that the drying is slow and a beautiful image cannot be obtained unless it is inevitably heated and dried as described above. Is done. [Ink sample 1] described in the patent document has a solid content exceeding 11% and 10% when calculated. However, since the resin contains a dispersant polymer and is not an emulsion type as in our present patent, the amount of resin is large. It is estimated that it cannot be added.

JP 2003-226827 A JP 2000-117960 A Japanese Patent Application No. 2005-241860 JP-A-4-139271 JP 2005-15672 A JP 2005-220352 A JP 2000-44858 A

  The present invention is capable of printing on plain paper and ink jet exclusive paper, and further is a non-porous substrate having a low water absorption capability such as a plastic sheet such as a polyester sheet, a plastic film laminated paper, a plastic surface sheet, or glass or metal. In addition, the present invention provides a water-based ink and medium set that does not select a medium that can be printed, and a printing method.

The said subject is solved by (1)-(29) of this invention.
(1) “A set of a recording ink containing at least a colorant, a water-dispersible resin, a wetting agent, a surfactant, and water, and a recording medium (media) for printing using the ink. The recording ink is suitable for direct recording on a non-porous substrate as a recording medium (medium), and the colorant and water-dispersible resin in the recording ink are used. The total content is 10 to 40% by mass in solid content, and the amount of resin in the total solid content is 60% by mass or more.
(2) “The amount of the wetting agent is 30% by weight or less, and further 20% by weight or less when drying in a short time is required,” for the inkjet according to the item (1) Set of ink and media ",
(3) “Set of ink-jet ink and media according to item (1), wherein the water-dispersible resin is a resin emulsion having a particle size of 50 to 200 nm”;
(4) “Set of ink-jet ink and medium according to any one of (1) to (3) above, wherein the colorant is a water-dispersible pigment”;
(5) “Set of ink-jet ink and medium according to any one of (1) to (3) above, wherein the colorant is a water-dispersible colorant”;
(6) The inkjet ink according to item (5), wherein the water-dispersible colorant is a polymer emulsion containing polymer fine particles containing a colorant that is insoluble or hardly soluble in water. Set with media ",
(7) “The surfactant contains at least one selected from silicone surfactants and fluorine surfactants, and the surface tension of the surfactant in the recording ink is 35 mN / m or less. A set of the ink-jet ink and the medium according to any one of (1) to (6),
(8) In any one of the above items (1) to (7), wherein the non-porous substrate is a plastic film sheet, a plastic film laminated paper, a plastic surface sheet, glass or metal. Set of ink-jet ink and media as described ",
(9) "The set of ink-jet ink and medium according to any one of (1) to (8) above, wherein the non-porous substrate is a polyester film",
(10) “At least a colorant, a water-dispersible resin, a wetting agent, a surfactant, and water are contained, and the total content of the colorant and the water-dispersible resin in the recording ink is a solid content. 10 to 40% by mass, the amount of resin in the total solid content is 60% by mass or more, and a recording ink suitable for direct recording on a non-porous substrate as a recording medium (medium) is contained in the container. Ink cartridges characterized by being housed in ",
(11) The above-mentioned (10), wherein the amount of the wetting agent in the recording ink is 30% by weight or less, and further 20% by weight or less when drying in a short time is required. Ink cartridge as described in section "
(12) “The ink cartridge according to item (10) or (11), wherein the water-dispersible resin in the recording ink is a resin emulsion having a particle size of 50 to 200 nm”;
(13) "The ink cartridge according to any one of (10) to (12), wherein the colorant in the recording ink is a water-dispersible pigment";
(14) "The ink cartridge according to any one of (10) to (12), wherein the colorant in the recording ink is a water-dispersible colorant",
(15) The items (10) to (10), wherein the water-dispersible colorant in the recording ink is a polymer emulsion in which polymer fine particles contain a colorant that is insoluble or hardly soluble in water. The ink cartridge according to any one of Items (14),
(16) “The surfactant in the recording ink contains at least one selected from silicone surfactants and fluorine surfactants, and the surface tension of the surfactant in the recording ink” The ink cartridge according to any one of (10) to (15), wherein the ink cartridge is 35 mN / m or less,
(17) In any one of (10) to (16), wherein the non-porous substrate is a plastic film sheet, a plastic film laminated paper, a plastic surface sheet, glass or metal. Described ink cartridges ",
(18) "The ink cartridge according to any one of (10) to (17) above, wherein the non-porous substrate is a polyester film",
(19) “At least a colorant, a water-dispersible resin, a wetting agent, a surfactant, and water are contained, and the total content of the colorant and the water-dispersible resin in the recording ink is a solid content. 10 to 40% by mass, the amount of resin in the total solid content is 60% by mass or more, and the recording ink for recording directly on a non-porous substrate as a recording medium (medium) Ink-jet printing method characterized by printing on a porous substrate and obtaining a recorded material ",
(20) The above-mentioned (19), wherein the amount of the wetting agent in the recording ink is 30% by weight or less, and further 20% by weight or less when drying in a short time is required. Inkjet printing method according to item ",
(21) “Inkjet printing method according to item (19) or (20), wherein the water-dispersible resin in the recording ink is a resin emulsion having a particle size of 50 to 200 nm” ,
(22) "The inkjet printing method according to any one of (19) to (21) above, wherein the colorant in the recording ink is a water-dispersible pigment",
(23) "The inkjet printing method according to any one of (19) to (21) above, wherein the colorant in the recording ink is a water-dispersible colorant";
(24) Items (19) to (19), wherein the water-dispersible colorant in the recording ink is a polymer emulsion in which polymer fine particles contain a colorant that is insoluble or hardly soluble in water. The inkjet printing method according to any one of Items (23), "
(25) “The surfactant in the recording ink contains at least one selected from a silicone surfactant and a fluorosurfactant, and the surface tension of the surfactant in the recording ink. The inkjet printing method according to any one of (19) to (24) above, wherein is 35 mN / m or less,
(26) In any one of the above (19) to (25), wherein the non-porous substrate is a plastic film sheet, a plastic film laminated paper, a plastic surface sheet, glass or metal. Described inkjet printing method ",
(27) "The inkjet printing method according to any one of (19) to (26) above, wherein the non-porous substrate is a polyester film",
(28) The item (19) to item (27), wherein when printing a solid part area having an area of 2 mm square or more, printing is performed with an interval of 10 seconds or more every 2 mm square printing. Inkjet printing method according to any one of "
(29) “After printing on the non-porous substrate made of plastic film sheet, plastic film laminated paper, plastic surface sheet, glass or metal, the image is dried by heating or / and blowing. The inkjet printing method according to any one of (19) to (28) "

According to the present invention, the wettability when printing on a plastic film such as polyester by increasing the solid content of the colorant and water-dispersible resin in the recording ink, increasing the resin ratio, and lowering the surface tension, Printing on the film medium with water-based ink without using a special device such as a heater by improving the drying and fixing properties and by reducing the amount of wetting agent as much as possible, and without using UV curable ink or oil-based ink It has become possible. However, heating is advantageous for high-speed drying.
In addition, when the ratio of the wetting agent is not so small (20% by mass to 30% by mass), heating is effective for quick drying because it is not so quick drying, but beading defects due to high viscosity at high solids concentration. Such image density bias is relatively small compared to low viscosity / low solid content ink. On the other hand, when the amount of the wetting agent is as small as 20% by mass or less, the viscosity is relatively low. There are few defects and high-speed drying is also possible. When the wetting agent is 10% or less, it becomes faster drying.
Specifically, due to the high solid content and the high resin ratio, the inkjet ink used in the inkjet ink and media set of the present invention, the ink cartridge, and the inkjet printing method can be dried even with a non-porous substrate sheet. Excellent fixability and image clarity.
In the ink used in the ink set of (2) and the medium, the ink cartridge of (11), and the ink jet printing method of (20), the wetting agent amount is 30% by mass or less in addition to the high solid content and the high resin concentration. Therefore, even with a non-porous substrate, it is possible to obtain a practical fixing property after being left for several days. Further, when the amount of the wetting agent is reduced to 20% by mass, the drying property is relatively improved. Even with a non-porous substrate, it is possible to obtain a drying property within a few minutes even without heat drying.
The injection reliability can be obtained even if a large amount of resin emulsion is added due to the resin emulsion particle size of (3) above.
The ink used in the above-mentioned (4) ink and media set, (13) ink cartridge, and (22) ink jet printing method is a pigment, and is excellent in light resistance and water resistance.
The pigment-based colorant is jetted by the ink set of (5) and (6) and the ink set of (6), the ink cartridge of (14) and (15), and the ink used in the inkjet printing method of (23) and (24). Excellent stability.
The ink used in the set of the ink (7) and the medium, the ink cartridge (16), and the ink used in the ink jet printing method (25) are excellent in drying property and leveling property.
The ink used in the above sets (1) to (7) is an ink having good drying and fixing properties without variation in image density due to liquid deviation such as beading.
The above (8) shows a medium effective as a non-porous substrate. However, it is not limited to this.
By the inkjet printing method of (28) above, density variation called beading due to liquid deviation is prevented even in a large area solid portion, and image clarity is improved.
By the inkjet printing method of (29) above, the drying property is further improved and high-speed printing is possible.
The ink and media set of (1) to (9) of the present invention is a set of ink and media having such a high solid content concentration, a high resin concentration, and a low wetting agent amount. The same applies to the set of ink and media in the ink cartridges (10) to (18) and the set of ink and media used in the printing ink jet printing methods (19) to (27).

The present invention is a recording ink containing at least a colorant, a water-dispersible resin, a wetting agent, a surfactant, and water, wherein the total content of the colorant and the water-dispersible resin in the recording ink is Printing on plastic sheet, plastic film laminated paper, plastic surface sheet, glass or metal using inkjet ink whose solid content is 10-40% by mass and the resin content in the total solid content is 60% by mass or more And a set of ink and media.
These inks can also be printed on printing paper such as plain paper, inkjet recording paper and gloss paper.
Further, increasing the solid content concentration improves the image quality / drying property, and increasing the resin content improves the fixing property.
Further, the drying property is further improved by setting the amount of the wetting agent to 30% by mass or less, preferably 20% by mass or less, more preferably 10% by mass or less.
When the amount of the wetting agent is 30 to 20% by mass, the quick-drying property is inferior, but because of the high solid content and the high resin concentration, the image is clear and has sufficient fixability unless it is left for several days or rubbed strongly by means of heating. can get. When the content is 10 to 20% by mass, sufficient fixability can be obtained in a few days even if no heating means is provided. When the amount of the wetting agent is 10% by mass or less, drying property and fixing property within several minutes can be obtained.
Moreover, since the colorant to be used is a polymer emulsion in which polymer fine particles contain a water-insoluble or poorly water-soluble colorant, injection reliability is high.
In addition, the recording ink of the present invention has a wettability to a medium in the above high viscosity ink by adding a silicone surfactant and a fluorine surfactant to make the surface tension 35 mN / m or less. -Leveling properties are improved, thereby improving drying properties. In particular, it can be used as ink that can be printed on plain paper.
Further, when printing a solid area having an area of 2 mm square or more, it is possible to eliminate unevenness in image density of the solid area by shifting the time and place for every 2 mm square printing.

(Ink for recording)
The recording ink of the present invention contains at least a colorant, a water-dispersible resin, a wetting agent, a surfactant, and water, and further contains other components as necessary.
In the present invention, by increasing the total solid content of the colorant and the water-dispersible resin contained in the recording ink, a rapid increase in viscosity is caused in the drying process after the ink has landed on the medium. ) And drying characteristics are improved.
The total content of the colorant and the water-dispersible resin in the recording ink is 10 to 40% by mass in solid content, and preferably 15 to 30% by mass. If the total content is less than 10% by mass, the amount of wetting agent must be increased in order to increase the viscosity of the ink in order to improve the image quality, resulting in poor drying and exceeding 40% by mass. In this case, since the drying property on the nozzle surface is increased, ejection failure may occur easily.

  Further, when compared with the same colorant amount, if only the colorant concentration is increased, the colorants strongly aggregate after fixing on the medium by ink jet, and the hue is greatly changed. Therefore, as the ratio of the water-insoluble resin to the colorant increases, the aggregation between the colorants is suppressed, and the coloring property of the colorant improves, and as the ratio of the water-insoluble resin increases, the fixability of the colorant to the medium also improves. To do. Therefore, the ratio of the resin to the solid content in the recording ink is desirably 60% by mass to 95% by mass. The resin here includes not only an emulsion of a resin added separately, but also a resin enclosing a colorant originally present in the colorant dispersion. When the resin ratio in the total solid content is less than 60% by mass, the fixing property and the color tone are inferior.

The surface tension of the recording ink is 35 mN / m or less, and more preferably 30 mN / m or less. Moreover, 15 mN / m or more is preferable and 20 mN / m or more is more preferable. When the surface tension exceeds 35 mN / m, the liquid is difficult to get wet with the medium. Also, if the surface tension is too low, ink wetting on the head nozzle surface becomes too strong, and meniscus formation may become unstable and cause ejection failure.
Here, the surface tension can be measured using, for example, a fully automatic surface tension meter (CBVP-Z, manufactured by Kyowa Interface Science Co., Ltd.).
The viscosity of the ink was measured at 25 ° C. using a viscometer (RL-500, manufactured by Toki Sangyo Co., Ltd.). If the viscosity is low when the viscosity is low, the liquid component will evaporate and dry quickly, and liquid unevenness will not occur.However, if there are many wetting agents and the liquid component is difficult to evaporate, the viscosity will be low. Since liquid unevenness tends to occur, it is preferably 5 mPas or more.
In any case, a high solid content concentration and a high resin concentration are effective in preventing image defects due to liquid deviation and improving the drying property.

[Colorant]
The colorant is preferably a water-dispersible colorant that is water-dispersible and contains a pigment.
Examples of the water dispersible colorant include (1) a pigment having at least one hydrophilic group on the surface and exhibiting at least one of water dispersibility and water solubility in the absence of the dispersant, and (2) polymer fine particles. And a polymer emulsion containing a water-insoluble or poorly water-soluble coloring material, (3) a pigment dispersed with a surfactant and a water-soluble polymer having a weight average molecular weight of 50,000 or less, and the like. .
Among these, a polymer emulsion in which the polymer fine particles (2) contain a colorant that is insoluble or hardly soluble in water is capable of being jetted relatively stably even at a low wetting agent concentration.
This pigment is characterized in that it can be stably printed without causing nozzle omission during printing even in an ink having a wetting agent concentration as low as 10% or less in order to improve drying properties.

In the water dispersible colorant of (2), the polymer emulsion containing a colorant is at least one of a polymer fine particle encapsulated with a pigment and a polymer fine particle having a pigment adsorbed on the surface thereof ( It may be a water-insoluble dye, not necessarily a pigment). In this case, it is not necessary that all the pigments are encapsulated and / or adsorbed, and the pigments may be dispersed in the emulsion as long as the effects of the present invention are not impaired.
Examples of the polymer that forms the polymer emulsion include vinyl polymers, polyester polymers, polyurethane polymers, polymers disclosed in JP-A Nos. 2000-53897 and 2001-139849, and the like. Among these, vinyl polymers and polyester polymers are particularly preferable.

There is no restriction | limiting in particular as said pigment, According to the objective, it can select suitably, For example, any of an inorganic pigment and an organic pigment may be sufficient.
Examples of the inorganic pigment include titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, chrome yellow, and carbon black. Among these, carbon black is preferable. In addition, as said carbon black, what was manufactured by well-known methods, such as a contact method, a furnace method, and a thermal method, is mentioned, for example.
Examples of the organic pigment include azo pigments, polycyclic pigments, dye chelates, nitro pigments, nitroso pigments, and aniline black. Among these, azo pigments and polycyclic pigments are more preferable. Examples of the azo pigment include azo lakes, insoluble azo pigments, condensed azo pigments, and chelate azo pigments. Examples of the polycyclic pigment include phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, and quinofullerone pigments. Examples of the dye chelate include a basic dye chelate and an acid dye chelate.

There is no restriction | limiting in particular as a color of the said coloring agent, According to the objective, it can select suitably, For example, the thing for black, the thing for color, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.
Examples of the black color include carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black, copper, iron (CI pigment black 11), oxidation, and the like. Examples thereof include metals such as titanium and organic pigments such as aniline black (CI Pigment Black 1).
Examples of the color are C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 17, 24, 34, 35, 37, 42 (yellow iron oxide), 53, 55, 74, 81, 83, 95, 97, 98, 100, 101, 104 , 408, 109, 110, 117, 120, 128, 138, 150, 151, 153, 183, C.I. I. Pigment orange 5, 13, 16, 17, 36, 43, 51, C.I. I. Pigment Red 1, 2, 3, 5, 17, 22, 23, 31, 38, 48: 2, 48: 2 (Permanent Red 2B (Ca)), 48: 3, 48: 4, 49: 1, 52: 2, 53: 1, 57: 1 (Brilliant Carmine 6B), 60: 1, 63: 1, 63: 2, 64: 1, 81, 83, 88, 101 (Bengara), 104, 105, 106, 108 ( Cadmium red), 112, 114, 122 (quinacridone magenta), 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 185, 190, 193, 209, 219, C.I. I. Pigment violet 1 (rhodamine lake), 3, 5: 1, 16, 19, 23, 38, C.I. I. Pigment Blue 1, 2, 15 (phthalocyanine blue), 15: 1, 15: 2, 15: 3 (phthalocyanine blue), 16, 17: 1, 56, 60, 63, C.I. I. Pigment green 1, 4, 7, 8, 10, 17, 18, 36, and the like.
The black pigment is preferably carbon black. As a black ink, carbon black is excellent in color tone, excellent in water resistance, light repellency, dispersion stability, and inexpensive.
Other pigment (for example, carbon) surface is treated with resin, etc. to make it dispersible in water, and pigment (for example, carbon) surface is added with a functional group such as sulfone group or carboxyl group and dispersed in water Processed pigments made possible can be used.
Further, the pigment may be included in the microcapsule so that the pigment can be dispersed in water.

[Wetting agent]
The wetting agent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butane Diol, 2,3-butanediol, 1,4-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, tetraethylene glycol, 1,6-hexanediol, 2-methyl-2 , 4-pentanediol, polyethylene glycol, 1,2,4-butanetriol, 1,2,6-hexanetriol and the like. These may be used individually by 1 type and may use 2 or more types together.

  The content of the wetting agent in the recording ink is advantageous in terms of drying when printing on a non-porous substrate such as a plastic surface film, and is usually 30% or less in the present invention. If it exceeds 30% by mass, the drying property is considerably poor. Preferably it is 20 mass% or less, More preferably, it is 15% mass or less, More preferably, it is 10 mass% or less, Most preferably, it is 5 mass% or less. However, this is not the case when auxiliary means such as a heating / air blowing means are provided for drying. In addition, up to about 30% by mass can be used as long as the method can be left to dry for one day or more, or heat-dried.

On the other hand, if the wetting agent is less than 10% by mass, when the carriage is operated for a long time and only the nozzles of that color are not printed while printing other colors, the nozzle portion of the non-printing color is dried. It may cause nozzle missing. At this time, it is necessary to frequently perform idle ejection to a place other than the recording medium, and at least once every time A4 printing is performed. If possible, it is desirable to perform idle ejection for every one line printing. In addition, supplying water into the cap that covers the nozzle part during a long-term stop is one means for preventing the nozzle part from drying.
As described above, it is preferable to maintain the ejection reliability of the ink with less wetting agent by mechanically enhancing the maintenance mechanism.
However, a polymer emulsion obtained by adding a water-insoluble or poorly water-soluble colorant to the polymer fine particle, which is a colorant used in the present invention, is relatively jet-stable even at a low wetting agent concentration. No maintenance mechanism is required.

[Surfactant]
The surfactant is not particularly limited, and can be appropriately selected from surfactants that do not impair dispersion stability, depending on the combination of the type of colorant, the wetting agent, and the water-soluble organic solvent. However, in order to improve the leveling property and improve the wettability, at least one selected from a silicone surfactant and a fluorine surfactant is preferable. Among these, a fluorine-based surfactant is particularly preferable. These are indispensable when they are used in common as ink that can be printed on plain paper.
Also, when printing on plastic surface sheets such as polyester sheets, reducing the surface tension with a surfactant improves wettability and leveling on the media surface, and improves drying and image quality uniformity. Have a good impact.

  Examples of the fluorosurfactant include a perfluoroalkyl sulfonic acid compound, a perfluoroalkyl carboxylic compound, a perfluoroalkyl phosphate compound, a perfluoroalkyl ethylene oxide adduct, and a perfluoroalkyl ether group in the side chain. And a polyoxyalkylene ether polymer compound. Among these, the polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain has a low foaming property, and the bioaccumulation property of a fluorine compound that has been regarded as a problem in recent years is low and highly safe. Particularly preferred.

Examples of the perfluoroalkyl sulfonic acid compound include perfluoroalkyl sulfonic acid and perfluoroalkyl sulfonate.
Examples of the perfluoroalkyl carboxylic compounds include perfluoroalkyl carboxylic acids and perfluoroalkyl carboxylic acid salts.
Examples of the perfluoroalkyl phosphate compound include perfluoroalkyl phosphate esters and perfluoroalkyl phosphate salts.
The polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain includes a polyoxyalkylene ether polymer having a perfluoroalkyl ether group in the side chain, and a polyoxyalkylene ether having a perfluoroalkyl ether group in the side chain. Examples thereof include a sulfate salt of a polymer and a salt of a polyoxyalkylene ether polymer having a perfluoroalkyl ether group in the side chain.
As counter ions of salts in these fluorosurfactants, Li, Na, K, NH ₄ , NH ₃ CH ₂ CH ₂ OH, NH ₂ (CH ₂ CH ₂ OH) ₂ , NH (CH ₂ CH ₂ OH) ₃ etc. are mentioned.

As said fluorosurfactant, what was synthesize | combined suitably may be used and a commercial item may be used.
Examples of the commercially available products include Surflon S-111, S-112, S-113, S-121, S-131, S-132, S-141, and S-145 (all manufactured by Asahi Glass Co., Ltd.), Fullrad FC. -93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431 (all manufactured by Sumitomo 3M), MegaFuck F-470, F1405, F-474 (All manufactured by Dainippon Ink & Chemicals, Inc.), Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, UR (all manufactured by DuPont), FT-110, FT- 250, FT-251, FT-400S, FT-150, FT-400SW (all manufactured by Neos Co., Ltd.), PF-151N (manufactured by Omninova) Among these, FT-110, FT-250, FT-251, FT-400S, manufactured by Neos Co., Ltd. from the viewpoint that the good print quality, particularly the color developability and the leveling property on paper are remarkably improved. FT-150, FT-400SW and OM-nova PF-151N are particularly preferred.
As specific examples of the fluorine-based surfactant, those represented by the following general formula are suitable.
(1) Anionic fluorosurfactant

ただし、前記一般式中、Ｒｆは、下記構造式で表わされるフッ素含有疎水基の混合物を表わす。Ａは、−ＳＯ_３Ｘ、−ＣＯＯＸ、又は−ＰＯ_３Ｘ（ただし、Ｘは対アニオンであり、具体的には、水素原子、Ｌｉ、Ｎａ、Ｋ、ＮＨ_４、ＮＨ_３ＣＨ_２ＣＨ_２ＯＨ、ＮＨ_２（ＣＨ_２ＣＨ_２ＯＨ）_２、又はＮＨ（ＣＨ_２ＣＨ_２ＯＨ）_３が挙げられる）を表わす。

In the general formula, Rf represents a mixture of fluorine-containing hydrophobic groups represented by the following structural formula. A is —SO ₃ X, —COOX, or —PO ₃ X (where X is a counter anion, specifically, a hydrogen atom, Li, Na, K, NH ₄ , NH ₃ CH ₂ CH ₂ OH, , NH ₂ (CH ₂ CH ₂ OH) ₂ , or NH (CH ₂ CH ₂ OH) ₃ ).

ただし、前記一般式中、Ｒｆ’は下記構造式で表わされるフッ素含有基を表わす。Ｘは、上記と同じ意味を表わす。ｎは１又は２の整数、ｍは２−ｎを表わす。

In the general formula, Rf ′ represents a fluorine-containing group represented by the following structural formula. X represents the same meaning as described above. n represents an integer of 1 or 2, and m represents 2-n.

ただし、ｎは３〜１０の整数を表わす。

However, n represents the integer of 3-10.

ただし、前記一般式中、Ｒｆ’及びＸは、上記と同じ意味を表わす基を表わす。

However, in the general formula, Rf ′ and X represent a group having the same meaning as described above.

ただし、前記一般式中、Ｒｆ’及びＸは、上記と同じ意味を表わす。
（２）ノニオン性フッ素系界面活性剤

In the general formula, Rf ′ and X have the same meaning as described above.
(2) Nonionic fluorosurfactant

ただし、前記一般式中、Ｒｆは、上記と同じ意味を表わす。ｎは５〜２０の整数を表わす。

However, in the general formula, Rf represents the same meaning as described above. n represents an integer of 5 to 20.

ただし、前記一般式中、Ｒｆ’は、上記と同じ意味を表わす。ｎは１〜４０の整数を表わす。
（３）両性フッ素系界面活性剤

In the general formula, Rf ′ represents the same meaning as described above. n represents an integer of 1 to 40.
(3) Amphoteric fluorosurfactant

ただし、前記一般式中、Ｒｆは、上記と同じ意味を表わす。
（４）オリゴマー型フッ素系界面活性剤

However, in the general formula, Rf represents the same meaning as described above.
(4) Oligomer type fluorosurfactant

ただし、前記一般式中、Ｒｆ”は、下記構造式で表わされるフッ素含有基を表わす。ｌは０〜１０の整数を表わす。Ｘは、上記と同じ意味を表わす。

In the general formula, Rf ″ represents a fluorine-containing group represented by the following structural formula. L represents an integer of 0 to 10. X represents the same meaning as described above.

ただし、ｎは１〜４の整数を表わす。

However, n represents the integer of 1-4.

ただし、Ｒｆ”は、上記と同じ意味を表わす。ｌは０〜１０の整数、ｍは０〜１０の整数、ｎは０〜１０の整数をそれぞれ表わす。

Rf ″ represents the same meaning as described above. L represents an integer of 0 to 10, m represents an integer of 0 to 10, and n represents an integer of 0 to 10.

The silicone surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, side chain modified polydimethylsiloxane, both terminal modified polydimethylsiloxane, one terminal modified polydimethylsiloxane, side Examples thereof include polydimethylsiloxane modified at both chain ends, and those using a polyoxyethylene group or a polyoxyethylene polyoxypropylene group as a modifying group exhibit good properties as an aqueous surfactant.
Such a surfactant can be easily obtained as a commercial product from Big Chemie Co., Ltd., Shin-Etsu Silicone Co., Ltd., Toray Dow Corning Silicone Co., Ltd., and the like.
The polyether-modified silicone surfactant is not particularly limited and may be appropriately selected depending on the purpose. For example, a polyalkylene oxide structure represented by the following structural formula is added to the side chain of the dimethylpolysiloxane in the Si part. Introduced compounds and the like.

ただし、前記構造式中、ｍ、ｎ、ａ、及びｂは整数を表わす。Ｒ及びＲ’はアルキル基、アルキレン基を表わす。
前記ポリエーテル変性シリコーン化合物としては、市販品を用いることができ、例えば、ＫＦ−６１８、ＫＦ−６４２、ＫＦ６４３（いずれも信越化学工業株式会社製）などが挙げられる。

However, m, n, a, and b represent the integer in the said structural formula. R and R ′ represent an alkyl group or an alkylene group.
A commercial item can be used as said polyether modified silicone compound, For example, KF-618, KF-642, KF643 (all are Shin-Etsu Chemical Co., Ltd. product) etc. are mentioned.

In addition to the fluorine surfactant and the silicone surfactant, anionic surfactants, nonionic surfactants, amphoteric surfactants, acetylene glycol surfactants, and the like can be used.
Examples of acetylene glycol surfactants include 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, , 5-dimethyl-1-hexyn-3-ol and the like. Examples of commercially available acetylene glycol surfactants include Surfynol 104, 82, 465, 485, and TG manufactured by Air Products (USA).
The surfactant is not limited to these, and may be used alone or in combination. Even if it is not easily dissolved by itself in the recording liquid, it can be solubilized by mixing and exist stably.

[Water dispersible resin]
There is no restriction | limiting in particular as said water dispersible resin, Although it can select suitably according to the objective, For example, a condensation type synthetic resin, an addition type synthetic resin, a natural polymer compound, etc. are mentioned.
Examples of the condensed synthetic resin include polyester resins, polyurethane resins, polyepoxy resins, polyamide resins, polyether resins, and silicon resins. Examples of the addition type synthetic resin include polyolefin resins, polystyrene resins, polyvinyl alcohol resins, polyvinyl ester resins, polyacrylic acid resins, unsaturated carboxylic acid resins, and the like. Examples of the natural polymer compound include celluloses, rosins, and natural rubber.
The water-dispersible resin may be used as a homopolymer, may be used as a copolymer and used as a composite resin, and any of a single-phase structure type, a core-shell type, and a power feed type emulsion Can be used.

As the water-dispersible resin, a resin itself having a hydrophilic group and having a self-dispersibility, and a resin itself having no dispersibility and imparted with a surfactant or a resin having a hydrophilic group can be used. . Among these, an emulsion of resin particles obtained by emulsion and suspension polymerization of an ionomer of a polyester resin or a polyurethane resin or an unsaturated monomer is optimal. Acrylic resin and acrylic silicon resin emulsion are also optimal. In the case of emulsion polymerization of an unsaturated monomer, the resin emulsion is reacted with water to which an unsaturated monomer, a polymerization initiator, a surfactant, a chain transfer agent, a chelating agent, a pH adjusting agent, and the like are added. Therefore, a water-dispersible resin can be easily obtained, and the resin properties can be easily changed, so that desired properties can be easily produced.
Examples of the unsaturated monomer include unsaturated carboxylic acids, (meth) acrylic acid ester monomers, (meth) acrylic acid amide monomers, aromatic vinyl monomers, vinyl cyanide compounds. A monomer, a vinyl monomer, an allyl compound monomer, an olefin monomer, a diene monomer, an oligomer having an unsaturated carbon, and the like can be used alone or in combination. By combining these monomers, the properties can be flexibly modified, and the properties of the resin can be modified by performing a polymerization reaction or a graft reaction using an oligomer type polymerization initiator.

Examples of the unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid and the like.
Examples of the monofunctional (meth) acrylic acid esters include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, and 2-ethylhexyl methacrylate. Octyl methacrylate, decyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, dimethylaminoethyl methacrylate, methacryloxyethyl trimethylammonium salt, 3 -Mekakuri Xylpropyltrimethoxysilane, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, decyl acrylate, Examples include dodecyl acrylate, octadecyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, glycidyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, dimethylaminoethyl acrylate, and acryloxyethyl trimethyl ammonium salt.

  Examples of the polyfunctional (meth) acrylic acid esters include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, and 1,4-butylene. Glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, dipropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, polybutylene glycol dimethacrylate, 2,2'-bis (4-methacryloxydiethoxyphenyl) ) Propane, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, polyethylene glycol Diacrylate, triethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, 1,9-nonanediol di Acrylate, polypropylene glycol diacrylate, 2,2′-bis (4-acryloxypropyloxyphenyl) propane, 2,2′-bis (4-acryloxydiethoxyphenyl) propane trimethylolpropane triacrylate, trimethylolethanetri Acrylate, tetramethylol methane triacrylate, ditrimethylol tetraacrylate, tetramethylol methane tetraacrylate, pentaerythritol tetraacrylate, dipen Such as erythritol hexaacrylate, and the like.

Examples of the (meth) acrylic acid amide monomers include acrylamide, methacrylamide, N, N-dimethylacrylamide, methylenebisacrylamide, 2-acrylamido-2-methylpropanesulfonic acid, and the like.
Examples of the aromatic vinyl monomers include styrene, α-methylstyrene, vinyltoluene, 4-t-butylstyrene, chlorostyrene, vinylanisole, vinylnaphthalene, divinylbenzene, and the like.
Examples of the vinylcyan compound monomers include acrylonitrile and methacrylonitrile.
Examples of the allyl compound monomers include allyl sulfonic acid salt thereof, allylamine, allyl chloride, diallylamine, diallyldimethylammonium salt, and the like.
Examples of the olefin monomers include ethylene and propylene.
Examples of the diene monomers include butadiene and chloroprene.
Examples of the vinyl monomers include vinyl acetate, vinylidene chloride, vinyl chloride, vinyl ether, vinyl ketone, vinyl pyrrolidone, vinyl sulfonic acid or salts thereof, vinyl trimethoxysilane, vinyl triethoxysilane, and the like.
Examples of the oligomers having unsaturated carbon include styrene oligomers having methacryloyl groups, styrene-acrylonitrile oligomers having methacryloyl groups, methyl methacrylate oligomers having methacryloyl groups, dimethylsiloxane oligomers having methacryloyl groups, and polyesters having acryloyl groups. An oligomer etc. are mentioned.
The water-dispersible resin has a strong alkalinity and strong acidity, and causes molecular breakage such as dispersion breakage and hydrolysis. Therefore, the pH is preferably 4 to 12, particularly from the viewpoint of miscibility with a water-dispersible colorant. As for pH, 6-11 are more preferable, and 7-9 are still more preferable.

The particle size of the water-dispersible resin is related to the viscosity of the dispersion. When the composition is the same, the smaller the particle size, the larger the viscosity at the same solid content. The average particle size of the water-dispersible resin is preferably 50 nm or more so as not to have an excessively high viscosity when converted into an ink. In addition, when the particle size is several tens of microns, it becomes larger than the nozzle opening of the ink jet head and cannot be used. It is known that if particles having a large particle diameter exist in the ink even if they are smaller than the nozzle opening, the ejection property is deteriorated. Therefore, the average particle diameter is more preferably 500 nm or less, and even more preferably 200 nm or less, in order not to inhibit the ink ejection properties.
In particular, in order to obtain a high image quality with a non-porous medium at a high resin fine particle concentration as in this patent, the resin fine particle diameter needs to be 50 to 200 nm.
The water-dispersible resin does not fluidize the water-dispersed colorant on the surface of the plastic recording medium (prevents image density unevenness (beading)) and fixes it on the medium surface or fixing aid It is preferable to improve the fixability of the coloring material by forming a film at room temperature. Therefore, the minimum film-forming temperature (MFT) of the water-dispersible resin is preferably normal temperature or lower, and more preferably 20 ° C. or lower.
Further, when the glass transition temperature of the water-dispersible resin is -40 ° C. or lower, the resin film becomes more viscous and the printed matter is tacky. Therefore, the water-dispersible resin has a glass transition temperature of −30 ° C. or higher. It is preferable.
The content of the water-dispersible resin in the recording ink is preferably 60% by mass or more and 95% by mass or less in the total solid content including the resin enclosing the colorant.

  The other components are not particularly limited and may be appropriately selected as necessary. For example, a pH adjuster, antiseptic / antifungal agent, chelating reagent, rust inhibitor, antioxidant, ultraviolet absorber, oxygen Examples include absorbers and light stabilizers.

  The pH adjuster is not particularly limited as long as it can adjust the pH to a desired value without adversely affecting the recording ink to be prepared, and can be appropriately selected according to the purpose. Examples include alcohol amines, alkali metal hydroxides, ammonium hydroxides, phosphonium hydroxides, and alkali metal carbonates.

  Examples of the alcohol amines include diethanolamine, triethanolamine, 2-amino-2-ethyl-1,3-propanediol, and the like.

  Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, and potassium hydroxide.

  Examples of the ammonium hydroxide include ammonium hydroxide, quaternary ammonium hydroxide, quaternary phosphonium hydroxide, and the like.

  Examples of the alkali metal carbonate include lithium carbonate, sodium carbonate, and potassium carbonate.

  Examples of the antiseptic / antifungal agent include sodium dehydroacetate, sodium sorbate, 2-pyridinethiol-1-oxide sodium, sodium benzoate, sodium pentachlorophenol, and the like.

  Examples of the chelating reagent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uramil diacetate, and the like.

  Examples of the rust inhibitor include acidic sulfite, sodium thiosulfate, ammonium thiodiglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite.

As the antioxidant, deterioration inhibitors for plastic materials and rubber materials can be used. For example, phenolic antioxidants (including hindered phenolic antioxidants), amine antioxidants, sulfur System antioxidant, phosphorus antioxidant and the like.
Examples of the phenolic antioxidant (including hindered phenolic antioxidant) include butylated hydroxyanisole, 2,6-di-tert-butyl-4-ethylphenol, stearyl-β- (3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 3,9-bis [1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) ) Propionyloxy] ethyl] 2,4,8,10-tetrixaspiro [5,5] undecane, 1,1,3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) Examples include benzene, tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate] methane.
Examples of the amine-based antioxidant include phenyl-β-naphthylamine, α-naphthylamine, N, N′-di-sec-butyl-p-phenylenediamine, phenothiazine, N, N′-diphenyl-p-phenylenediamine. 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butylphenol, 2,4-dimethyl-6-tert-butyl-phenol, butylhydroxyanisole, 2,2′-methylenebis ( 4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), tetrakis [methylene -3 (3,5-di-tert-butyl-4-dihydroxyphenyl) propionate Methane, 1,1,3-tris (2-methyl-4-hydroxy -5-tert-butylphenyl) butane and the like.
Examples of the sulfur-based antioxidant include dilauryl 3,3′-thiodipropionate, distearyl thiodipropionate, lauryl stearyl thiodipropionate, dimyristyl 3,3′-thiodipropionate, and distearyl β. , Β′-thiodipropionate, 2-mercaptobenzimidazole, dilauryl sulfide and the like.
Examples of the phosphorus antioxidant include triphenyl phosphite, octadecyl phosphite, triisodecyl phosphite, trilauryl trithiophosphite, and trinonylphenyl phosphite.

Examples of the ultraviolet absorber include a benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber, a salicylate ultraviolet absorber, a cyanoacrylate ultraviolet absorber, and a nickel complex ultraviolet absorber.
Examples of the benzophenone-based ultraviolet absorber include 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-methoxybenzophenone. 2,2 ′, 4,4′-tetrahydroxybenzophenone and the like.
Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole and the like.
Examples of the salicylate-based ultraviolet absorber include phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate, and the like.
Examples of the cyanoacrylate ultraviolet absorber include ethyl-2-cyano-3,3′-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate, and butyl-2- And cyano-3-methyl-3- (p-methoxyphenyl) acrylate.
Examples of the nickel complex ultraviolet absorber include nickel bis (octylphenyl) sulfide, 2,2′-thiobis (4-tert-octylferrate) -n-butylamine nickel (II), 2,2′-thiobis. (4-tert-octylferrate) -2-ethylhexylamine nickel (II), 2,2′-thiobis (4-tert-octylferrate) triethanolamine nickel (II) and the like.

  The recording ink of the present invention uses an piezoelectric head as a pressure generating means for pressurizing ink in an ink flow path as an ink jet head, and deforms a diaphragm that forms the wall surface of the ink flow path to increase the volume in the ink flow path. A so-called piezo type that discharges ink droplets by changing (see Japanese Patent Laid-Open No. 2-51734), or a so-called thermal type that generates bubbles by heating ink in an ink flow path using a heating resistor. (Refer to Japanese Patent Application Laid-Open No. 61-59911), a diaphragm that forms the wall surface of an ink flow path and an electrode are arranged to face each other, and the diaphragm is deformed by an electrostatic force generated between the diaphragm and the electrode. Thus, a printer on which any ink jet head such as an electrostatic type (see Japanese Patent Laid-Open No. 6-71882) for discharging ink droplets by changing the volume of the ink flow path is mounted. It is also good to use in the printer.

  The recording ink of the present invention can be suitably used in various fields, and can be suitably used in an image forming apparatus (printer or the like) based on an ink jet recording method. The recording ink is heated at 50 to 200 ° C. and can be used for a printer or the like having a function of accelerating print fixing. The following ink cartridge, ink recorded matter, ink jet recording apparatus, and ink jet recording method of the present invention It can be particularly preferably used.

(ink cartridge)
The ink cartridge of the present invention contains the recording ink of the present invention in a container, and further includes other members and the like appropriately selected as necessary.
The container is not particularly limited, and its shape, structure, size, material, etc. can be appropriately selected according to the purpose. For example, an ink formed of a plastic container, an aluminum laminate film, a resin film, etc. Suitable examples include those having at least a bag.

Next, the ink cartridge will be described with reference to FIGS. Here, FIG. 1 is a view showing an example of the ink cartridge of the present invention, and FIG. 2 is a view including a case (exterior) of the ink cartridge of FIG.
As shown in FIG. 1, the ink cartridge (200) is filled into the ink bag (241) from the ink inlet (242) and exhausted, and then the ink inlet (242) is closed by fusion. In use, the needle of the apparatus main body is pierced into the ink discharge port (243) made of a rubber member and supplied to the apparatus.
The ink bag (241) is formed of a packaging member such as a non-permeable aluminum laminate film. As shown in FIG. 2, the ink bag (241) is usually housed in a plastic cartridge case (244) and is detachably mounted on various ink jet recording apparatuses.
The ink cartridge of the present invention contains the recording ink (ink set) of the present invention and can be used by being detachably mounted on various ink jet recording apparatuses. It is particularly preferable to use it by mounting it.

[Inkjet recording apparatus and inkjet recording method]
The ink jet recording apparatus of the present invention includes at least ink flying means, and further includes other means appropriately selected as necessary, for example, stimulus generation means, control means, and the like.
The ink jet recording method of the present invention includes at least an ink flying process, and further includes other processes appropriately selected as necessary, for example, a stimulus generation process, a control process, and the like.
The ink jet recording method of the present invention can be preferably carried out by the ink jet recording apparatus of the present invention, and the ink flying step can be suitably carried out by the ink flying means. Moreover, the said other process can be suitably performed by the said other means.

[Ink flying process and ink flying means]
The ink flying step is a step of recording an image by applying a stimulus to the recording ink of the present invention and causing the recording ink to fly.
The ink flying means is means for recording an image by applying a stimulus to the recording ink of the present invention and causing the recording ink to fly. The ink flying means is not particularly limited, and examples thereof include various nozzles for ejecting ink.
In the present invention, it is preferable that at least a part of the liquid chamber portion, the fluid resistance portion, the vibration plate, and the nozzle member of the inkjet head is formed of a material containing at least one of silicon and nickel.
The nozzle diameter of the inkjet nozzle is preferably 30 μm or less, and preferably 1 to 20 μm.
In addition, it is preferable that a sub tank for supplying ink is provided on the ink jet head, and the sub tank is replenished with ink from an ink cartridge through a supply tube.

The stimulus can be generated, for example, by the stimulus generating means, and the stimulus is not particularly limited and can be appropriately selected according to the purpose, such as heat (temperature), pressure, vibration, light, etc. Is mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, heat and pressure are preferable.
Examples of the stimulus generating means include a heating device, a pressurizing device, a piezoelectric element, a vibration generating device, an ultrasonic oscillator, and a light. Specifically, for example, a piezoelectric actuator such as a piezoelectric element, heat generation, and the like. Examples include a thermal actuator that uses a phase change caused by film boiling of a liquid using an electrothermal transducer such as a resistor, a shape memory alloy actuator that uses a metal phase change caused by a temperature change, and an electrostatic actuator that uses an electrostatic force.

  There are no particular restrictions on the manner in which the recording ink flies, and it varies depending on the type of the stimulus. For example, when the stimulus is “heat”, a recording signal is output to the recording ink in the recording head. Corresponding thermal energy is applied using, for example, a thermal head, bubbles are generated in the recording ink by the thermal energy, and the recording ink is formed into droplets from the nozzle holes of the recording head by the pressure of the bubbles. For example, a discharge injection method may be used. Further, when the stimulus is “pressure”, for example, by applying a voltage to a piezoelectric element bonded to a position called a pressure chamber in an ink flow path in the recording head, the piezoelectric element bends and the volume of the pressure chamber is increased. And the recording ink is ejected and ejected as droplets from the nozzle holes of the recording head.

The size of the recording ink droplets to be ejected is preferably 2 to 40 pl, the ejection speed is preferably 6 to 20 m / s, and the driving frequency is preferably 1 kHz or more. The resolution is preferably 300 dpi or more.
In addition, it is preferable that ink is ejected to either the print area or the non-print area before moisture evaporation near the nozzle exceeds 30%.

  The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as sequencers and computers.

One embodiment for carrying out the ink jet recording method of the present invention by the ink jet recording apparatus of the present invention will be described with reference to the drawings.
The ink jet recording apparatus shown in FIG. 3 has an apparatus main body (101), a paper feed tray (102) for loading paper mounted on the apparatus main body (101), and an image mounted on the apparatus main body (101). A paper discharge tray (103) for stocking (formed) paper and an ink cartridge loading section (104) are provided. Using this paper feed tray (102), it was possible to feed plastic sheets such as polyester sheets.
On the upper surface of the ink cartridge loading section (104), an operation section (105) such as operation keys and a display is arranged. The ink cartridge loading section (104) has an openable / closable front cover (115) for attaching and detaching the ink cartridge (200).

  As shown in FIGS. 4 and 5, a guide rod (131), which is a guide member horizontally mounted on left and right side plates (not shown), and a stay (132) are provided in the apparatus main body (101). 133) is slidably held in the main scanning direction, and is moved and scanned in the direction of the arrow in FIG. 5 by a main scanning motor (not shown).

The carriage (133) includes a recording head (134) including four inkjet recording heads that eject recording ink droplets of each color of yellow (Y), cyan (C), magenta (M), and black (Bk). Are arranged in a direction crossing the main scanning direction and the ink droplet discharge direction is directed downward.
As an inkjet recording head constituting the recording head (134), a piezoelectric actuator such as a piezoelectric element, a thermal actuator that utilizes a phase change caused by liquid film boiling using an electrothermal transducer such as a heating resistor, and a temperature change A shape memory alloy actuator using a metal phase change, an electrostatic actuator using an electrostatic force, or the like provided as an energy generating means for discharging recording ink can be used.
The carriage (133) is equipped with a sub tank (135) for each color for supplying ink of each color to the recording head (134). The sub-tank (135) is supplied with the recording ink of the present invention from the ink cartridge (200) of the present invention loaded in the ink cartridge loading section (104) via a recording ink supply tube (not shown). Is done.

  On the other hand, as a paper feeding unit for feeding the paper (142) stacked on the paper stacking unit (pressure plate) (141) of the paper feed tray (102), 1 sheet (142) is fed from the paper stacking unit (141). A half-moon roller (sheet feeding roller 143) that separates and feeds the sheets one by one and a separation pad (144) made of a material having a large friction coefficient are provided opposite to the sheet feeding roller (143). The roller (143) is urged.

  A conveying belt (151) for electrostatically adsorbing and conveying the paper (142) as a conveying unit for conveying the paper (142) fed from the paper feeding unit below the recording head (134). A counter roller (152) for conveying the paper (142) sent from the paper supply unit via the guide (145) between the conveying belt (151) and a paper (substantially vertically upward) ( 142) and a leading guide roller 153 urged toward the conveying belt (151) by the holding member (154). (155) and a charging roller (156) which is a charging means for charging the surface of the conveyor belt (151).

  The conveyance belt (151) is an endless belt, is stretched between the conveyance roller (157) and the tension roller (158), and can circulate in the belt conveyance direction. The transport belt (151) includes, for example, a surface layer serving as a sheet adsorbing surface formed of a resin material having a thickness of about 40 μm that is not subjected to resistance control, for example, a copolymer of tetrafluoroethylene and ethylene (ETFE), It has the same material as the surface layer and a back layer (medium resistance layer, earth layer) that has been subjected to resistance control by carbon. On the back side of the conveyance belt (151), a guide member (161) is arranged corresponding to the printing area by the recording head (134). As a paper discharge unit for discharging the paper (142) recorded by the recording head (134), a separation claw (171) for separating the paper (142) from the transport belt (151), and paper discharge A roller (172) and a paper discharge roller (173) are provided, and a paper discharge tray (103) is arranged below the paper discharge roller (172).

  A double-sided paper feeding unit (181) is detachably attached to the back surface of the apparatus main body (101). The double-sided paper feeding unit (181) takes in the paper (142) returned by the reverse rotation of the transport belt (151), reverses it, and feeds it again between the counter roller (152) and the transport belt (151). . A manual paper feed unit (182) is provided on the upper surface of the double-sided paper feed unit (181).

In this ink jet recording apparatus, the sheet (142) is separated and fed one by one from the sheet feeding unit, and the sheet (142) fed substantially vertically upward is guided by the guide (145) and the transport belt (151). ) And the counter roller (152). Further, the leading end is guided by the conveying guide (153) and pressed against the conveying belt (151) by the leading end pressure roller (155), and the conveying direction is changed by about 90 °.
At this time, the conveyance belt (157) is charged by the charging roller (156), and the paper (142) is electrostatically adsorbed to the conveyance belt (151) and conveyed. Therefore, by driving the recording head (134) according to the image signal while moving the carriage (133), ink droplets are ejected onto the stopped sheet (142) to record one line, and the sheet ( 142) is carried a predetermined amount, and then the next line is recorded. Upon receiving a recording end signal or a signal that the rear end of the paper (142) has reached the recording area, the recording operation is finished and the paper (142) is discharged to the paper discharge tray (103).
When the recording ink remaining amount near end in the sub tank (135) is detected, a required amount of recording ink is supplied from the ink cartridge (200) to the sub tank (135).

  In this ink jet recording apparatus, when the recording ink in the ink cartridge (200) of the present invention is used up, the casing of the ink cartridge (200) can be disassembled and only the ink bag inside can be replaced. Further, the ink cartridge (200) can supply recording ink stably even when the ink cartridge (200) is vertically placed and has a front loading configuration. Therefore, even when the upper part of the apparatus main body (101) is closed and installed, for example, even when it is stored in a rack or an object is placed on the upper surface of the apparatus main body (101), the ink The cartridge (200) can be easily replaced.

Here, an example is described in which the present invention is applied to a serial (shuttle type) ink jet recording apparatus that is scanned by a carriage.
Further, the ink jet recording apparatus and the ink jet recording method of the present invention can be applied to various kinds of recording by the ink jet recording method. It can be particularly preferably applied.

[Recording medium]
As the recording medium in the present invention, a non-porous substrate such as a plastic film sheet, a plastic film laminated paper, a plastic surface sheet, glass or metal is selected. It is a medium that does not have the water absorption capability of ordinary water-based inkjet recording paper.
For example, plastic films such as polyester films and sheets, polyolefin films and sheets are included as target media. Here, for example, a PET film is usually a mixture of about 10% or less inorganic fine particle filler, and therefore the plastic surface film used in the present invention is not necessarily formed of a plastic material. It is. Further, the plastic surface sheet that can be used in the present invention is a film having a plastic surface such as a plastic film laminated paper, a resin processed paper that is coated or impregnated with a plastic material and the paper surface is covered with the plastic material. It may be a sheet.
A water-absorbing material is applied to a general inkjet OHP sheet, but the present invention enables printing on a non-water-absorbing sheet that is not coated with such a material.
The ink can also be printed on glass, metal and the like.
On the other hand, the ink of the present invention is a water-based ink that does not select a medium and can be printed not only on these plastic media but also on paper such as general inkjet exclusive paper, high-quality paper, or printing gloss paper.

Examples of the present invention will be described below, but the present invention is not limited to these examples.
(Production Example 1)
-Preparation of polymer solution A-
After sufficiently replacing the inside of a 1 L flask equipped with a mechanical stirrer, thermometer, nitrogen gas inlet tube, reflux tube, and dropping funnel, 11.2 g of styrene, 2.8 g of acrylic acid, 12.0 g of lauryl methacrylate Then, 4.0 g of polyethylene glycol methacrylate, 4.0 g of styrene macromer, and 0.4 g of mercaptoethanol were mixed and heated to 65 ° C.
Next, 100.8 g of styrene, 25.2 g of acrylic acid, 108.0 g of lauryl methacrylate, 36.0 g of polyethylene glycol methacrylate, 60.0 g of hydroxylethyl methacrylate, 36.0 g of styrene macromer, 3.6 g of mercaptoethanol, azobismethylvalero A mixed solution of 2.4 g of nitrile and 18 g of methyl ethyl ketone was dropped into the flask over 2.5 hours. After dropping, a mixed solution of 0.8 g of azobismethylvaleronitrile and 18 g of methyl ethyl ketone was dropped into the flask over 0.5 hours. After aging at 65 ° C. for 1 hour, 0.8 g of azobismethylvaleronitrile was added, and further aging was performed for 1 hour. After completion of the reaction, 364 g of methyl ethyl ketone was added to the flask to prepare 800 g of polymer solution A having a concentration of 50% by mass.

-Preparation of dimethylquinacridone pigment-containing polymer fine particle water dispersion-
Next, 28 g of the obtained polymer solution A, C.I. I. 42 g of CI Pigment Red 122, 13.6 g of a 1 mol / L potassium hydroxide aqueous solution, 20 g of methyl ethyl ketone, and 13.6 g of ion-exchanged water were sufficiently stirred, and then kneaded using a roll mill. The obtained paste was put into 200 g of pure water and sufficiently stirred, and then the methyl ethyl ketone and water were distilled off using an evaporator, and the magenta polymer fine particles of Production Example 1 containing 15% by mass of pigment and 20% by mass of solid were prepared. An aqueous dispersion was prepared.

(Production Example 2)
-Preparation of copper phthalocyanine pigment-containing polymer fine particle dispersion-
In Production Example 1, C.I. I. An aqueous dispersion of cyan polymer fine particles was prepared in the same manner as in Production Example 1 except that Pigment Red 122 was changed to a copper phthalocyanine pigment and the pigment was further changed to 12% and 20% by mass.

(Production Example 3)
-Preparation of monoazo yellow pigment-containing polymer fine particle dispersion-
In Production Example 1, C.I. I. An aqueous dispersion of yellow polymer fine particles was prepared in the same manner as in Production Example 1 except that Pigment Red 122 was changed to Pigment Pigment Yellow 74 and the pigment content was 12% and the solid content was 20% by mass.

(Production Example 4)
-Preparation of polymer fine particle dispersion B (acrylic silicone emulsion)-
After fully replacing the inside of a 1 L flask equipped with a mechanical stirrer, thermometer, nitrogen gas inlet tube, reflux tube, and dropping funnel, 8.0 g of Latemul S-180 and 350 g of ion exchange water were added and mixed. The temperature was raised to 65 ° C. After temperature increase, 3.0 g of reaction initiator t-butyl peroxobenzoate and 1.0 g of sodium isoascorbate were added, and after 5 minutes, 45 g of methyl methacrylate, 160 g of 2-ethylhexyl methacrylate, 5 g of acrylic acid, butyl methacrylate 45 g, 30 g of cyclohexyl methacrylate, 15 g of vinyltriethoxysilane, 8.0 g of Latemul S-180, and 340 g of ion-exchanged water were mixed and dropped over 3 hours. Then, after heat aging at 80 ° C. for 2 hours, the mixture was cooled to room temperature and the pH was adjusted to 7-8 with sodium hydroxide. Ethanol was distilled off using an evaporator and the water content was adjusted to prepare 730 g of the polymer dispersion B solution of Production Example 4 having a solid content of 40% by mass.
The particle size of the resin fine particles was approximately 130 nm (measured at 23 ° C.). The particle size was measured using a particle size distribution measuring device UPA150 manufactured by Microtrack Co., Ltd. at a dilution ratio of 500 times.

The recording ink was produced according to the following procedure.
(Example 1-1)
Magenta ink having the following formulation: Magenta pigment-containing polymer fine particle dispersion of Production Example 1 (solid content 20%) 32% by mass
Emulsion resin aqueous solution of production example 4 (solid content 40%) 36% by mass
Glycerin 3% by mass
Fluorosurfactant (FS-300 manufactured by DuPont) 2.5% by mass
Antiseptic and fungicidal agent (Zeneca Proxel LV) 0.05% by mass
Amine-based pH adjuster 0.6% by mass
Silicone defoamer 0.1% by mass
Residual water Viscosity: 3.03 m · Pas, surface tension: 24.8 mN / m, total solid content: 21%, resin content in total solid content: 77%

(Example 1-2)
A cyan ink was prepared in the same manner except that the dispersion of Example 1-1 was changed to the copper phthalocyanine pigment-containing polymer fine particle dispersion of Production Example 2.
Viscosity: 2.78 mPas, surface tension: 24.3 mN / m, total solids: 21%, resin content in total solids: 82%

(Example 1-3)
A yellow ink was prepared in the same manner except that the dispersion of Example 1-1 was changed to the monoazo yellow pigment-containing polymer fine particle dispersion of Production Example 3.
Viscosity: 2.85 mPas, surface tension: 24.7 mN / m, total solids: 21%, resin content in total solids: 82%

(Example 2-1)
A magenta ink was prepared in the same manner as in Example 1-1 except that the amount of glycerin in Example 1-1 was changed to 13% by mass.
Viscosity: 4.41 mPas, surface tension: 24.5 mN / m

(Example 2-2)
A cyan ink was prepared in the same manner as in Example 1-2 except that the amount of glycerin in Example 1-2 was changed to 13% by mass.
Viscosity: 4.00 mPas, surface tension: 24.6 mN / m

(Example 2-3)
A yellow ink was prepared in the same manner as in Example 1-3 except that the amount of glycerin in Example 1-3 was changed to 13% by mass.
Viscosity: 4.1 mPas, surface tension: 24.3 mN / m

(Example 3-1)
A magenta ink was prepared in the same manner as in Example 1-1 except that the amount of glycerin in Example 1-1 was changed to 28% by mass.
Viscosity: 8.71 mPas, surface tension: 24.1 mN / m

(Example 3-2)
A cyan ink was prepared in the same manner as in Example 1-2 except that the amount of glycerin in Example 1-2 was changed to 28% by mass.
Viscosity: 8.07 mPas, surface tension: 23.8 mN / m

(Example 3-3)
A yellow ink was prepared in the same manner as in Example 1-3 except that the amount of glycerin in Example 1-3 was changed to 28% by mass.
Viscosity: 8.26 mPas, surface tension: 23.5 mN / m

Sets the ink of Examples 1-1 to 1-3 (ink set I), or Examples 2-1 to 2-3 (ink set II), or Examples 3-1 to 3-3 (ink set III) Then, printing was performed with a Ricoh manufactured inkjet printer G-707.
The medium is obtained by cutting a polyester film (trade name Lumirror 75-T60 manufactured by Toray Industries Inc.) into A4 size.

<Polyester film printing evaluation-drying evaluation 1>
Print a solid image of about 2mm square secondary colors (green, red, blue) in a variety of modes and put it in various modes, and attach Advantech filter paper 5A to the image area. The time at which it did not adhere to the surface was defined as the drying end time.
As a result, the ink set I did not adhere to the filter paper in about 150 seconds even when the ink was printed (secondary color-green) in the mode where the adhesion amount was 20 g / m ² . Further, the fixing property was sufficient with respect to the eraser and the finger touch. The solid image portion had a uniform density for the sake of clarity. As for the characters, clear characters with good fixability were obtained.
On the other hand, in ink set II, drying did not end for 20 minutes or more even with a small amount of adhesion of about 8 g / m ² . Ink set III had a longer drying time. Also, it took more than a day for the fixability of the eraser and finger touch to improve.
However, even in the ink sets II and III, the fixing property is improved after several days, and is not necessarily usable depending on the purpose.
Moreover, if a drying process using a dryer or a microwave oven is added, drying is completed in a short time even for ink sets II and III.

<Polyester film printing evaluation-drying evaluation 2>
Instead of the solid image of the dryness evaluation 1, a solid image of 1 cm square was printed and the dryness was evaluated.
As a result, in the ink set I, when printing was performed at an adhesion amount of 20 g / m ² , drying from the peripheral part took 5 minutes or more to dry the central part. Furthermore, a portion having a high image density toward the central portion and the diagonal portion of the square was formed.
In order to avoid this, a solid image of about 2 mm square was printed by sequentially printing the solid part printing even at time and place, and a fairly uniform solid image was obtained.

<Gloss paper printing evaluation>
Printing was performed on Oji Paper Co., Ltd. POD gloss coat 100 g / m ² paper. The amount of transfer of pure water to a recording medium at a contact time of 100 ms measured with a dynamic scanning absorption meter of this paper is 3.1 ml / m ² and the transfer of pure water to a recording medium at a contact time of 400 ms. The amount was 3.5 ml / m ² .
The drying times of ink sets I, II, and III are as shown in FIG.
Thus, even in the gloss paper for printing having a relatively low water absorption, a difference in drying property due to the amount of humectant (glycerin) appears. In both cases, the image quality was good. However, when the amount of ink adhering is large, ink with a large amount of wetting agent such as ink set III tends to generate shading (referred to as beading) in the solid image portion.

<Evaluation of plain paper stamp>
Ricoh manufactured plain paper Copied under the trade name T6200.
In the case of plain paper, the back surface density becomes high and hinders double-sided copying. However, as shown in FIG. 7, the ink set I having a glycerin amount of 3% has an image quality for double-sided copying with a low back surface density instead of the surface density. It was.

(Comparative Examples 1-1 to 1-3)
Inks were prepared in the same manner except that the addition amount of the emulsion resin aqueous solution (solid content 40%) of Production Example 4 in the inks of Examples 1-1 to 1-3 was 10% by mass. In this case, the total solid content is 10%, and the ratio of the resin in the total solid content is 54 (magenta) to 63% (cyan, yellow).
In this case, when printing on a polyester film, drying was slow because the total solid content was small, and the fixability was poor because the resin ratio in the solid content was small, and the image was not clear. The same was true when the addition amount of the emulsion resin aqueous solution (solid content 40%) of Production Example 4 of Examples 3-1 to 3-3 was 10% by mass (in the case of glycerin 28%).

(Comparative Example 2)
The following pigment surfactant dispersion was prepared.
C. I. Pigment Blue 15: 3 (100 g), polyoxyethylene oleyl ether ammonium sulfate (24.8 g), pure water (175.2 g) and the above were mixed, dispersed in a wet sand mill, 414.3 g of pure water was added, and the mixture was centrifuged. Coarse particles were removed by treatment to obtain a cyan pigment dispersion containing 14% pigment and 17.5% solids.
The pigment surfactant dispersion was used in place of the cyan pigment dispersion of Example 1-2. The surfactant pigment-dispersed ink with a small amount of wetting agent has poor jetting stability.

(Example 4-1)
Magenta dispersion of Production Example 1 (solid content 20%) 32% by mass
Emulsion of Production Example 4 (solid content 40%) 50% by mass
1.3-butanediol 2% by mass
Glycerin 3% by mass
2-ethyl-1,3-hexanediol 2% by mass
Fluorosurfactant 1% by mass
Amine-based pH adjuster 0.6% by mass
Silicone defoamer 0.1% by mass
Antiseptic and fungicide 0.05% by mass
Residual water Viscosity: 5.49 mPas, Surface tension: 24.3 mN / m, Solid content: 26%, Resin in solid content: 82%, Wetting agent: 5% by mass

(Example 4-2)
Instead of the magenta dispersion of Example 4-1, the cyan dispersion of Production Example 2 was used.
Viscosity: 5.17 mPas, surface tension: 24.7 mN / m, solid content: 26%, resin in solid content: 86%, wetting agent: 5% by mass

(Example 4-3)
Instead of the magenta dispersion of Example 4-1, the yellow dispersion of Production Example 3 was used, and instead of the fluorosurfactant, a polyether-modified silicone surfactant (manufactured by Shin-Etsu Chemical Co., Ltd., product name: KF-) 642).
Viscosity: 5.22 mPas, Surface tension: 25.2 mN / m, Solid content: 26%, Resin in solid content: 86%, Wetting agent: 5% by mass

  As described above, Examples 4-1 to 4-3 had a low wetting agent amount as in Example 1, and thus the polyester sheet dried quickly.

(Example 5-1)
The following ink is prepared: Magenta dispersion of Production Example 1 (solid content is about 20%) 42% by mass
Concentrated resin emulsion of Production Example 4 to a solid content of 55% (solid content 55%)
42.8% by mass
1.3-butanediol 11.5% by mass
Glycerin 3.8% by mass
2-ethyl-1,3-hexanediol 1% by mass
Fluorine-based surfactant 2% by mass
Amine-based pH adjuster 0.6% by mass
Silicone defoamer 0.1% by mass
Antiseptic and fungicide 0.05% by mass
Remaining water

(Example 5-2)
The dispersion of Example 5-1 is cyan of Production Example 2 (solid content is about 20%)
(Example 5-3)
The dispersion of Example 5-1 is Yellow of Production Example 3 (solid content is about 20%)

(Example 6-1)
The amount of the pigment dispersion of Example 5-1 (solid content is about 20%) is 38% by mass, 1.3-butanediol is 19.3% by mass, and glycerin is 6.5% by mass.
(Example 6-2)
The amount of the pigment dispersion (solid content is about 20%) of Example 5-2 is 38% by mass, 1.3-butanediol is 19.3% by mass, and glycerin is 6.5% by mass.
(Example 6-3)
The amount of the pigment dispersion (solid content is about 20%) in Example 5-3 is 38% by mass, 1.3-butanediol is 19.3% by mass, and glycerin is 6.5% by mass.
The solid content and wetting agent amount of each ink are shown below.

Printing was performed with the Ricoh manufactured inkjet printer G-707 using the ink of Example 5. The medium is obtained by cutting a polyester film (trade name Lumirror 75-T60 manufactured by Toray Industries Inc.) into A4 size.
When the ink of Example 5 was printed on a 1 cm square green solid portion, when the drying property was observed with a filter paper 5A manufactured by Advantech, adhesion of the filter paper almost disappeared in about 5 minutes unless pressed firmly. In addition, the fixing property was good for those that had been processed for 1 day unless they were rubbed strongly.
In addition, the solid portion was an image with little liquid deviation (beading). This is because the wetting agent is relatively small at approximately 15% and the solid content is as large as 31%.
Since the ink of Example 6 has a large amount of wetting agent, the drying property is relatively slower than that of Example 5, but after 3 days, an image could not be taken unless the solid part was rubbed strongly. Since the solid content is smaller than that of Example 5, the liquid unevenness (beading) at the large solid portion is relatively likely to occur, but the non-solid small area and characters can be printed without any problem on the image. . Compared to Example 5, the amount of wetting agent increased and the jetting stability was good. However, even in Example 5, nozzle omission that occurs after being left for one day or more is recovered by cleaning, and printing can be performed without any problem depending on the application.

As described above, these high solid content and high resin concentration inks have a quick drying property so that the ink does not adhere to the filter paper even if the filter paper is strongly pressed within a few minutes if the wetting agent is less than about 10% by mass. . When the content is 10 to 20% by mass, sufficient fixability can be obtained in a few days even if no heating means is provided. In addition, a large amount of ink does not adhere to the filter paper unless it is pressed firmly even after a few minutes after printing. When the wetting agent is 20 to 30% by mass, fixing and drying in several minutes is difficult, but after standing for several days, a large amount of resin works and the fixing property is improved. In this case, a heating means such as a microwave oven is effective for fixing in a short time. If the wetting agent exceeds 30% by mass, it does not have a practical drying property unless heated and dried.
These inks can be printed on non-porous substrates such as glass and metal.
In particular, there is no problem on the image in the case of only character printing.

It is the schematic which shows an example of the ink cartridge of this invention. FIG. 2 is a schematic view including a case (exterior) of the ink cartridge of FIG. 1. FIG. 4 is a perspective explanatory view showing a state where an ink cartridge loading unit cover of the ink jet recording apparatus is opened. It is a schematic block diagram explaining the whole structure of an inkjet recording device. It is a schematic block diagram which shows an example of the inkjet head of this invention. It is a figure which shows the drying time of each ink set. It is a figure which shows a plain paper printing evaluation result.

Explanation of symbols

101 apparatus main body 102 paper feed tray 103 paper discharge tray 104 ink cartridge loading unit 105 operation unit 111 upper cover 112 front surface 115 front cover 131 guide rod 132 stay 133 carriage 134 recording head 135 sub tank 141 paper placement unit 142 paper 143 paper supply roller 144 Separator Pad 145 Guide 151 Conveyor Belt 152 Counter Roller 153 Conveyor Guide 154 Pressing Member 155 Tip Pressure Roller 156 Charging Roller 157 Conveying Roller 158 Densation Roller 161 Guide Member 171 Separation Claw 172 Discharge Roller 173 Discharge Roller 181 Double-sided Paper Feed Unit 182 Manual paper feed unit 200 Ink cartridge 241 Ink bag 242 Ink inlet 243 Ink outlet 244 Cartridge exterior (case)

Claims (29)

A set of a recording ink containing at least a colorant, a water-dispersible resin, a wetting agent, a surfactant, and water, and a recording medium (medium) for printing using the ink, The recording ink is suitable for direct recording on a non-porous substrate as a recording medium (medium), and the total content of the colorant and the water-dispersible resin in the recording ink is A set of inkjet ink and media, characterized in that the solid content is 10 to 40% by mass, and the amount of resin in the total solid content is 60% by mass or more. 2. The ink jet ink and media set according to claim 1, wherein the amount of the wetting agent is 30% by weight or less, and further 20% by weight or less when drying in a short time is required. The ink-jet ink and media set according to claim 1, wherein the water-dispersible resin is a resin emulsion having a particle size of 50 to 200 nm. The ink-jet ink and media set according to any one of claims 1 to 3, wherein the colorant is a water-dispersible pigment. The ink-jet ink and media set according to any one of claims 1 to 3, wherein the colorant is a water-dispersible colorant. 6. The ink-jet ink and media set according to claim 5, wherein the water-dispersible colorant is a polymer emulsion containing polymer fine particles containing a water-insoluble or hardly water-soluble colorant. The surfactant includes at least one selected from silicone surfactants and fluorine surfactants, and the surface tension of the surfactant in the recording ink is 35 mN / m or less. A set of the ink-jet ink and media according to any one of claims 1 to 6. The ink-jet ink and media set according to any one of claims 1 to 7, wherein the non-porous substrate is a plastic film sheet, a plastic film laminated paper, a plastic surface sheet, glass or metal. The ink-jet ink and media set according to any one of claims 1 to 8, wherein the non-porous substrate is a polyester film. At least a colorant, a water-dispersible resin, a wetting agent, a surfactant, and water are contained, and the total content of the colorant and the water-dispersible resin in the recording ink is 10 to 40 mass in solid content. The amount of resin in the total solid content is 60% by mass or more, and a recording ink suitable for direct recording on a non-porous substrate as a recording medium (medium) is contained in a container. An ink cartridge characterized by comprising: 11. The ink cartridge according to claim 10, wherein the amount of the wetting agent in the recording ink is 30% by weight or less, and 20% by weight or less when drying in a short time is required. The ink cartridge according to claim 10 or 11, wherein the water-dispersible resin in the recording ink is a resin emulsion having a particle diameter of 50 to 200 nm. The ink cartridge according to claim 10, wherein the colorant in the recording ink is a water-dispersible pigment. The ink cartridge according to claim 10, wherein the colorant in the recording ink is a water-dispersible colorant. The water-dispersible colorant in the recording ink is a polymer emulsion in which polymer fine particles contain a colorant that is insoluble or hardly soluble in water. ink cartridge. The surfactant in the recording ink contains at least one selected from silicone surfactants and fluorosurfactants, and the surface tension of the surfactant in the recording ink is 35 mN / m. The ink cartridge according to any one of claims 10 to 15, wherein: The ink cartridge according to any one of claims 10 to 16, wherein the non-porous substrate is a plastic film sheet, a plastic film laminated paper, a plastic surface sheet, glass or metal. The ink cartridge according to claim 10, wherein the non-porous substrate is a polyester film. At least a colorant, a water-dispersible resin, a wetting agent, a surfactant, and water are contained, and the total content of the colorant and the water-dispersible resin in the recording ink is 10 to 40 mass in solid content. %, The amount of resin in the total solid content is 60% by mass or more, and the non-porous substrate using a recording ink for recording directly on the non-porous substrate as a recording medium (medium) An ink-jet printing method characterized in that a printed matter is obtained by printing. 20. The ink jet printing method according to claim 19, wherein the amount of the wetting agent in the recording ink is 30% by weight or less, and further 20% by weight or less when drying in a short time is required. . 21. The inkjet printing method according to claim 19, wherein the water-dispersible resin in the recording ink is a resin emulsion having a particle size of 50 to 200 nm. The ink-jet printing method according to any one of claims 19 to 21, wherein the colorant in the recording ink is a water-dispersible pigment. The inkjet printing method according to any one of claims 19 to 21, wherein the colorant in the recording ink is a water-dispersible colorant. The water-dispersible colorant in the recording ink is a polymer emulsion in which polymer fine particles contain a colorant that is insoluble or sparingly soluble in water. Inkjet printing method. The surfactant in the recording ink contains at least one selected from silicone surfactants and fluorosurfactants, and the surface tension of the surfactant in the recording ink is 35 mN / m. The inkjet printing method according to any one of claims 19 to 24, wherein: 26. The ink jet printing method according to claim 19, wherein the non-porous substrate is a plastic film sheet, a plastic film laminated paper, a plastic surface sheet, glass or metal. 27. The ink jet printing method according to claim 19, wherein the non-porous substrate is a polyester film. The inkjet printing method according to any one of claims 19 to 27, wherein when printing a solid area having an area of 2 mm square or more, printing is performed with an interval of 10 seconds or more every 2 mm square printing. 20. The method according to claim 19, wherein the image is heated and / or blown and dried after printing on the non-porous substrate made of plastic film sheet, plastic film laminated paper, plastic surface sheet or glass or metal. 28. The inkjet printing method according to any one of 28.

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