JP4806173B2 - Emulsion ink for ink jet, ink cartridge, ink recorded matter, ink jet recording apparatus and ink jet recording method - Google Patents

Description

  In the present invention, clogging resistance, ejection stability, fine line reproducibility (feathering), image density, color reproducibility, color boundary bleeding (color bleed), back-through, quick drying, ink storage stability (= ejection) The present invention relates to an emulsion ink for inkjet which is excellent in all of (stability), abrasion resistance, light resistance, water resistance and moisture resistance, and an ink cartridge, an ink record, an inkjet recording apparatus and an inkjet recording method using the ink.

Inkjet printers are rapidly spreading, including personal use, because they are low noise, low cost, and capable of full color printing.
As an ink used for such an ink jet printer, for example, a water-soluble dye is dissolved in water and a water-soluble organic solvent (see Patent Document 1 and Patent Document 2), and a pigment is dispersed in water and a water-soluble organic solvent. And the like (see Patent Document 3 and Patent Document 4).

  However, these are all water-based inks, and are liable to solidify or increase in viscosity due to evaporation of moisture, and cannot be said to have essentially good clogging resistance and ejection stability. Further, the water-soluble dye has few coloring components remaining on the paper after the ink is dried, and it is essentially difficult to improve the image density. Furthermore, regardless of dye-based or pigment-based, water-based inks are always concerned about solidification due to evaporation of moisture. For this reason, it is difficult to increase the solid content, and it is also necessary to use a humectant, that is, a nonvolatile water-soluble organic solvent. The fact that the solid content cannot be used means that it is difficult to control the ink viscosity. As a result, the ink viscosity is set to be low, the ink penetration speed is increased, the ink is easily blotted, and the dot reproducibility (= color reproducibility) is poor. Color bleeding is likely to occur (color bleed). Further, if the discharge amount of ink having a high ink permeation rate is excessive, a back-through problem also occurs. Furthermore, the non-volatile water-soluble organic solvent added to prevent solidification deteriorates the ink drying property on paper, makes handling immediately after printing difficult, deteriorates dot reproducibility (= color reproducibility), and blurs color boundaries (color (Bleed), also spurred the problem of strikethrough. In addition, the solid content cannot be used, that is, the polymer pigment dispersant and the polymer film-forming agent cannot be used, which also causes problems in the storage stability of the ink (= occurrence of pigment aggregation) and abrasion resistance. It is likely to occur. Furthermore, since water-soluble dyes are dissolved in water in the molecular state or are present on paper, they easily discolor and have a serious drawback in light resistance. Of course, the water-soluble dye has a high solubility in water, and as a result, has a drawback that the water resistance and moisture resistance of the printed matter are poor.

  On the other hand, non-aqueous oil-based inks are also used as inkjet inks. Among them, the use of a volatile organic solvent as a main component is limited due to the problems of flammability and VOC (volatile organic compounds). Non-volatile organic solvents, so-called oil-based inks, are essentially excellent in clogging resistance and ejection stability because the ink itself is non-volatile. However, the oil-based ink mainly composed of this non-volatile organic solvent (so-called oil) cannot easily be expected to evaporate and dry the ink on paper. , Dot reproducibility (= color reproducibility), color boundary bleeding (color bleed), and back-through problems are also likely to occur. In addition, when an oil-soluble dye is used as a colorant, the oil-soluble dye as a colorant is dissolved in oil in a molecular state or is present on paper, so that fading easily occurs and there is a serious drawback in light resistance.

  Therefore, so far, clogging resistance, ejection stability, fine line reproducibility (feathering), image density, dot reproducibility (= color reproducibility), color boundary bleeding (color bleed), back-through, quick drying, There are many problems with ink storage stability (= ejection stability), abrasion resistance, light resistance, water resistance, moisture resistance, etc., and ink jet inks and related technologies that satisfy all of them have not been provided yet. Is the current situation.

Japanese Patent Laid-Open No. 5-124220 Japanese Patent Laid-Open No. 5-17715 JP-A-5-263028 JP-A-6-306317

  This invention is made | formed in view of this present condition, and makes it a subject to solve the said various problems in the past and to achieve the following objectives. That is, the present invention provides clogging resistance, ejection stability, fine line reproducibility (feathering), image density, color reproducibility, color-bleeding blur (color bleed), anti-back-through, handling immediately after printing, ink Ink-jet emulsion ink having excellent storage stability (= ejection stability), rubbing resistance, light resistance, water resistance, and moisture resistance, and ink cartridge, ink recorded matter, and inkjet recording apparatus using the ink It is another object of the present invention to provide an ink jet recording method.

Means for solving the problems are as follows. That is,
<1> A nonionic surfactant having HLB 3 to 5 as an oil component and an emulsifier having an oil phase of 10 to 90% by mass and an aqueous phase of 90 to 10% by mass and having an initial boiling point of 290 ° C. or higher. It is the emulsion ink for inkjets characterized by containing.
<2> The inkjet ink according to <1>, wherein the oil component is a vegetable oil-modified ester having an iodine value of 100 or less.
<3> The inkjet ink according to any one of <1> to <2>, wherein the nonionic surfactant of HLB 3 to 5 is a polyglycerin hydroxy fatty acid ester.
<4> The inkjet emulsion ink according to any one of <1> to <3>, further including an oil-soluble resin in the oil phase.
<5> The ink-jet emulsion ink according to any one of <1> to <4>, wherein the water phase contains at least water and a water-soluble organic solvent.
<6> The ink-jet emulsion ink according to any one of <1> to <5>, wherein a pigment is contained in at least one of an oil phase and an aqueous phase.
<7> An ink cartridge comprising the ink-jet emulsion ink according to any one of <1> to <6>, contained in a container.
<8> It has at least an ink flying unit that forms an image by applying a stimulus to the ink jet emulsion ink according to any one of <1> to <6> and causing the ink jet emulsion ink to fly. Inkjet recording apparatus.
<9> The inkjet recording apparatus according to <8>, wherein the stimulus is at least one selected from heat (temperature), pressure, vibration, and light.
<10> It includes at least an ink flying step of forming an image by applying a stimulus to the inkjet emulsion ink according to any one of <1> to <6> and flying the inkjet emulsion ink. This is an ink jet recording method.
<11> The inkjet recording method according to <10>, wherein the stimulus is at least one selected from heat (temperature), pressure, vibration, and light.
<12> An ink recording product comprising an image formed using the inkjet emulsion ink according to any one of <1> to <6> on a recording medium.

  The ink-jet emulsion ink of the present invention has at least an oil phase composed of an oil component having an initial boiling point of 290 ° C. or higher and an emulsifier, and an aqueous phase composed of at least water and a water-soluble organic solvent. By being an emulsion ink for water-in-oil type (= W / O) ink jet of 10 to 90% by mass, the ink in the ink jet recording apparatus, the ink jet head nozzle, or the clogging prevention unit part is assumed to be centered on the water in the ink. Even if the volatile component is lost, the oil component of the oil phase that is the outer phase is present, so that the ink is not solidified and clogging or ejection failure is unlikely to occur. This is similar to the fact that the ink mainly composed of a nonvolatile organic solvent (so-called oil) becomes non-volatile, and therefore has excellent clogging resistance and ejection stability. In addition, when ink is printed while containing moisture in the ink, that is, when the ink reaches the paper, it can be expected to evaporate and dry the ink moisture on the paper. Compared to the non-volatile organic solvent so-called oil-based ink, Water-type (= W / O) ink-jet emulsion inks are excellent in quick-drying properties. As a result, it is excellent in handling properties immediately after printing, and excellent in dot reproducibility (= thin line reproducibility, color reproducibility), color-resistant boundary bleeding (color bleed), and back-through resistance.

  In this case, since the water-in-oil (= W / O) emulsion stabilizes the emulsion, the oil component in the oil phase contains a vegetable oil-modified ester having an iodine value of 100 or less, and the emulsifier is a nonionic interface of HLB 3-5. It is preferred to include an activator. This is because, in order to obtain a stable water-in-oil (= W / O) emulsion, a nonionic surfactant of HLB 3 to 5 which is dissolved in the oil phase and retains hydrophilicity is desirable. This is because it is desirable that the lipophilic group of the nonionic surfactant of HLB 3 to 5 is affinity and stretched in the oil phase with a solvent having high solubility, that is, a vegetable oil-modified monoester. The stretched lipophilic group forms steric hindrance on the surface of the internal phase (here, the aqueous phase), preventing contact, adhesion and coalescence between the internal phase and the internal phase, and a water-in-oil (= W / O) emulsion. To stabilize. If the oil phase is composed mainly of a weakly soluble solvent, such as paraffinic oil, without using a solubilizing agent, it is not possible to expect the lipophilic group to grow. No steric hindrance is formed, contact between the inner phase and the inner phase, adhesion, and coalescence occur, and the water-in-oil (= W / O) emulsion becomes unstable.

  In addition, even if the volatile components centered on moisture in the ink are lost, the oil component of the oil phase that is the outer phase is present, so there is a degree of freedom in the use of solids. It is preferable to include an oil-soluble resin in the oil phase that is the outer phase of the emulsion. This is because ink viscosity is controlled, that is, bleeding is controlled, dot reproducibility (= fine line reproducibility, color reproducibility) is improved, and color boundary bleeding (color bleeding) and back-through can be prevented. Furthermore, by including an oil-soluble resin in the oil phase, it means that the use of a polymeric pigment dispersant and a polymeric film-forming agent is permitted, and the storage stability of the ink (= preventing pigment aggregation from occurring). In addition, the abrasion resistance can be improved.

  In addition, when an oil-soluble or water-soluble dye is used as the colorant, the dye as the colorant is dissolved in oil or water in the molecular state, or is present on paper, so it is easy to fade and seriously affects light resistance. There are some disadvantages. Furthermore, when a water-soluble dye is used as the colorant, the dye as the colorant is water-soluble in the first place, so that it easily dissolves again in water or moisture, and has serious drawbacks in water resistance and moisture resistance. is there. Therefore, in the present invention, it is preferable to include a pigment in either the oil phase or the aqueous phase. This is because the pigment is a particle formed by aggregating colorant molecules, so even if the colorant molecules on the surface of the particles fade, there are unbleached molecules below the faded molecules, and the entire pigment particle If you see, fading is avoided. Furthermore, since the pigments are overlapped on the printed paper or paper fiber as a pigment aggregate, even if the uppermost pigment particles are faded, unbleached pigment particles are present under the faded pigment particles. It exists, and if you look at the entire print, fading is avoided. By using a pigment in this way, light resistance is improved. In addition, since pigments are particles formed by aggregation of colorant molecules, they are difficult to dissolve in water or moisture, and there are pigments that overlap as pigment aggregates on printed paper or paper fibers. It is robust against water or moisture and provides sufficient water resistance and moisture resistance. The use of a dye for adjusting the color tone and ensuring transparency is not limited at all.

In order to further stabilize the water-in-oil (= W / O) emulsion, it is preferable to use a polyglycerin hydroxy fatty acid ester as a nonionic surfactant of HLB 3 to 5 as an emulsifier. As the nonionic surfactant of HLB 3 to 5, a very large number of molecular structures can be considered, and in particular, an emulsion in which polyglycerin hydroxy fatty acid ester is highly stable can be obtained. This is because polyglycerin hydroxy fatty acid ester has a relatively large hydrophilic group among commercially available nonionic surfactants, and the hydrophilic group has a strong affinity for an aqueous phase and a relatively large lipophilicity. The oleophilic group forms a thick steric hindrance layer on the surface of the aqueous phase because it has a group, and a hydroxyl group in the middle of the straight chain attracts the oleophilic group to form a dense steric hindrance layer It is thought that it is because it is doing.
Therefore, clogging resistance, ejection stability, fine line reproducibility (feathering), image density, color reproducibility, resistance to color boundary bleeding (color bleed), back-through, handling immediately after printing, ink storage stability (= Ejection stability), Abrasion resistance, light resistance, water resistance, and moisture resistance can be provided.

  The ink cartridge of the present invention comprises the recording ink of the present invention contained in a container. The ink cartridge is suitably used for a printer using an ink jet recording method. When recording is performed using ink contained in the ink cartridge, clogging resistance, ejection stability, fine line reproducibility (feathering), image density, color reproducibility, color-bleeding blur (color bleed), High image quality excellent in all of through-through, handling properties immediately after printing, ink storage stability (= ejection stability), abrasion resistance, light resistance, water resistance, and moisture resistance can be obtained.

  The ink jet recording apparatus of the present invention has at least ink flying means for forming an image by applying energy to the recording ink of the present invention and causing the recording ink to fly. In the ink jet recording apparatus, the ink flying means applies energy to the recording ink of the present invention and causes the recording ink to fly to form an image. As a result, clogging resistance, ejection stability, fine line reproducibility (feathering), image density, color reproducibility, color boundary bleeding (color bleed), anti-back-through, handling immediately after printing, ink storage stability High-quality image formation excellent in all of the properties (= ejection stability), abrasion resistance, light resistance, water resistance, and moisture resistance is possible.

  The ink jet recording method of the present invention includes at least an ink flying step of forming an image by applying energy to the recording ink of the present invention and causing the recording ink to fly. In the ink jet recording method, in the ink flying step, energy is applied to the recording ink of the present invention, and the recording ink is ejected to form an image. As a result, clogging resistance, ejection stability, fine line reproducibility (feathering), image density, color reproducibility, color boundary bleeding (color bleed), anti-back-through, handling immediately after printing, ink storage stability High-quality image formation excellent in all of the properties (= ejection stability), abrasion resistance, light resistance, water resistance, and moisture resistance is possible.

  The inkjet recorded matter of the present invention comprises an image formed on the recording medium using the recording ink of the present invention. In the ink jet recording, clogging resistance, ejection stability, fine line reproducibility (feathering), image density, color reproducibility, color-bleeding blur (color bleed), anti-back-through, handling immediately after printing, A high image quality excellent in all of the storage stability (= ejection stability), rubbing resistance, light resistance, water resistance and moisture resistance of the ink is maintained on the recording medium.

  According to the present invention, conventional problems can be solved, clogging resistance, ejection stability, fine line reproducibility (feathering), image density, color reproducibility, color-resistant boundary bleeding (color bleed), and back-through resistance. In addition, it is possible to provide an inkjet emulsion ink that is excellent in handling properties immediately after printing, ink storage stability (= ejection stability), abrasion resistance, light resistance, water resistance, and moisture resistance.

(Emulsion ink for inkjet)
The ink-jet emulsion ink of the present invention comprises 10 to 90% by mass of an oil phase and 90 to 10% by mass of an aqueous phase. The oil component having an initial boiling point of 290 ° C. or higher and an emulsifier of HLB 3 to 5 are contained in the oil phase. It contains an ionic surfactant, and further contains other components as required.

In this case, the emulsion ink for inkjet includes 10 to 90% by mass of an oil phase and 90 to 10% by mass of an aqueous phase, and preferably 20 to 40% by mass of an oil phase and 60 to 80% by mass of an aqueous phase.
When the mixing ratio of the oil phase is less than 10% by mass, the drying property on the printer is increased and clogging is likely to occur, and when it exceeds 90% by mass, the drying property on the recording paper is decreased, Set-off and hand-rubbing may occur easily.

<Oil phase>
The oil phase of the emulsion ink for inkjet includes at least an oil component having an initial boiling point of 290 ° C. or higher and a nonionic surfactant of HLB 3 to 5 as an emulsifier, an oil-soluble resin, a pigment, and further if necessary. , And other components such as a pigment dispersant, a gelling agent, an antioxidant, an extender pigment, and a dye.

-Oil component-
The oil component is not particularly limited as long as the initial boiling point is 290 ° C. or higher (preferably 300 ° C. or higher), and can be appropriately selected within a range that does not impair storage stability and the like. A solvent, synthetic oil, vegetable oil, vegetable oil modified ester, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. In addition, when using 2 or more types of oil components together, the initial boiling point of a mixed oil component is 290 degreeC or more, and 300 degreeC or more is preferable.
When the initial boiling point of the oil component is lower than 290 ° C., the oil component starts to volatilize, and the so-called VOC problem may become apparent.
Among the oil components, vegetable oil-modified esters having an iodine value of 100 or less (preferably 95 or less) are suitable from the viewpoint of storage stability of the emulsion ink for inkjet.

As the mineral oil, paraffinic oil, naphthenic oil, spindle oil, machine oil, lubricating oil, and the like are suitable, and commercially available products may be used.
Examples of the paraffinic oil include the Gargo Oil Arctic Series (1010, 1022, 1032, 1046, 1068, 1100, 3032, 3046, 3068, etc.) manufactured by Mobil Oil; Nippon Oil Spar Oil manufactured by Nippon Oil Corporation Series (B, C, D, E, etc.); Idemitsu Kosan Diana Process Oil (PX-32, PX-90, PW-32, PW-90, PW-380, PS-32, PS-90, PS -430), Diana Fresia series (S-32, S-90, P-32, P-90, P-150, P-180, P-430, etc.).
Examples of the naphthenic oil include Gargo Oil Arctic Oil 155 and 300ID manufactured by Mobil Oil, Gargo Oil Arctic Oil Light and Gargo Oil Arctic Oil C Heavy; Diana Process Oil (NP-24) manufactured by Idemitsu Kosan Co., Ltd. , NR-26, NR-68, NS-90S, NM-280, etc.), Diana Fresia series (N-28, N-90, N-150, U-46, U-56, U-68, U-130) U-170, U-260); Sansen Oil Series (410, 420, 450, 480, 3125, 4240, etc.) manufactured by Nippon San Oil Co., Ltd., and the like.

  Examples of the petroleum solvent include a part of Isopar series and Exol series manufactured by Exxon Chemical; a part of AF Solvent Series manufactured by Nippon Oil Corporation.

  Examples of the synthetic oil include polybutene, poly-α-olefin, alkyl aromatic, polyglycol, pentaphenyl ether, alkyl diphenyl ether, diester, polyol ester, and the like. Examples of the polybutene include hydrogenation grades (0H, 5H) manufactured by Idemitsu Kosan Co., Ltd .; (LV-7, LV-10, LV-25, LV-50, LV-100) manufactured by Nippon Oil Corporation. Can be mentioned. Examples of the poly-α-olefin include PAO series (5002, 5004, 5006, 5008, 5010) manufactured by Idemitsu Kosan Co., Ltd. and Shinflud series (201, 401, 601, 801) manufactured by Nippon Steel Chemical Co., Ltd. Is mentioned. Examples of the alkyl aromatic include alkene series (20T, 22, 100P, 68, 200P) manufactured by Nippon Oil Chemical Co., Ltd. Examples of the polyglycol include hot bearing oil (No. 200, No. 255) manufactured by Sato Special Oil Co., Ltd. Examples of the pentaphenyl ether include S-3105 manufactured by Matsumura Oil Research Institute. Examples of the alkyl diphenyl ether include Moresco High Loop Series (LB-15, LB-22, LB-32, LB-46, LB-68, LB-100) manufactured by Matsumura Oil Research Institute. Examples of the diester include an ester series (H2906, H2911, H2910, H2901, H2850) manufactured by Nippon Steel Chemical Co., Ltd., a polyol ester, for example, an ester series (H2962, H2915, H3855, H3895 manufactured by Nippon Steel Chemical Co., Ltd.). H5150, H5068, H5005) and the like.

  Examples of the vegetable oil include linseed oil, tall oil, corn oil, olive oil, rapeseed oil, castor oil, dehydrated castor oil, soybean oil, coconut oil and the like from various companies.

As the vegetable oil-modified ester, a vegetable oil-modified ester having an iodine value of 100 or less is particularly preferable. For example, methyl ester, isopropyl ester, butyl ester, isobutyl ester, 2-ethylhexanol (octyl) ester and the like are preferable.
Examples of the methyl ester include # 2012-98, # 2014-95, # 2016-95, # 2018-95, # 2180-80, # 3050, # 3000, # 3100, # 3120 manufactured by Toei Chemical Co., Ltd. AG Environmental Products, L .; L. C. Examples include Soy Gold 1000, Soy Gold 1100, Soy Gold 1500, and Soy Gold 2000. Examples of the isopropyl ester include # 4014 and # 4016 manufactured by Toei Chemical Co., Ltd. Examples of the butyl ester include # 4001, # 4002, # 4120, # 4160, and # 4200 manufactured by Toei Chemical Co., Ltd. Examples of the isobutyl ester include # 4014 and # 4016 manufactured by Toei Chemical Co., Ltd. Examples of the 2-ethylhexanol (octyl) ester include # 5001, # 5168, # 5100, # 5100-80 and # 5090 manufactured by Toei Chemical Co., Ltd.
In consideration of safety, it is preferable to use those oil components whose polycyclic aromatic components, which are aromatic hydrocarbons containing three or more condensed aromatic rings, are less than 3% by mass. Further, the mutagenicity index MI is less than 1.0, the aroma content (% C _A ) is 20 to 55%, the aniline point is 100 ° C. or less, and benzo [a] anthracene, benzo [ b] The content of polycyclic aromatics such as fluoranthene, benzo [j] fluoranthene, benzo [k] fluoranthene, benzo [a] pyrene, dibenzo [a, j] acridine is 10 ppm or less, and the total content is 50 ppm or less.
If necessary, highly safe aromatic oils (for example, see JP-A-11-80640) can also be used.

  The addition amount of the oil component having an initial boiling point of 290 ° C. or higher is preferably 60% by mass or more, and more preferably 70 to 99% by mass based on the total oil phase component in the ink. If the added amount of the oil component is less than 60% by mass, the amount of the oil component becomes too large, which may cause a problem of volatility.

-Emulsifier-
As the emulsifier, HLB 3-5 nonionic surfactant is used. If a nonionic surfactant having an HLB not satisfying 3 to 5 is used, the emulsifying ability to form a W / O emulsion is low, and it may not be emulsified.
Examples of the nonionic surfactant include sorbitan fatty acid esters such as sorbitan monooleate, sorbitan sesquioleate, and sorbitan monostearate; polyoxyethylene such as polyoxyethylene sorbitan monooleate and polyoxyethylene sorbitan trioleate. Ethylene sorbitan fatty acid ester; (poly) glycerin fatty acid ester such as glyceryl monostearate, decaglyceryl trioleate, hexaglycerin polyricinoleate; polyoxyethylene glycerin fatty acid such as polyoxyethylene sorbit fatty acid ester, polyoxyethylene glycerin vegetable oil fatty acid ester Esters: Polyethylene glycol fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers Le, polyoxyethylene alkyl amine fatty acid amides, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, higher alcohols, and the like. These may be used individually by 1 type and may use 2 or more types together.
As the nonionic surfactant of HLB 3 to 5, polyglycerin hydroxy fatty acid ester is particularly preferable. Specific examples include hexaglycerin polyricinoleate, and commercially available products include, for example, Nikko Chemicals Co., Ltd. Examples thereof include PR15 (HLB3.5) manufactured by the same company.

-Oil-soluble resin-
Examples of the oil-soluble resin contained in the oil phase include rosin resins such as rosin, polymerized rosin, hydrogenated rosin, rosin ester, rosin polyester resin, hydrogenated rosin ester; rosin-modified alkyd resin, rosin-modified maleic acid Resin, rosin modified resin such as rosin modified phenol resin; maleic acid resin; phenol resin; petroleum resin; rubber derivative resin such as cyclized rubber, terpene resin, alkyd resin, polymerized castor oil, and the like. These may be used individually by 1 type and may use 2 or more types together.
Examples of the rosin-modified phenol resin include Tamanoru 353, Tamanoru 403, Tamanoru 361, Tamanoru 387, Tamanoru 340, Tamanoru 400, Tamanoru 396, Tamanoru 354, KG836, KG846, KG1834, and KG1801 manufactured by Arakawa Chemical Industries, Ltd. Can be mentioned.

  The weight average molecular weight (Mw) of the oil-soluble resin is preferably 30,000 to 150,000, more preferably 55,000 to 150,000, from the viewpoint of fixability and printability. Further, these resins are preferably resins having a solubility of 1 g / g or more with respect to the Nisseki No. 0 solvent (1 g or more of No. 0 solvent is compatible with 1 g of resin). Moreover, 2-50 mass% of an oil phase is preferable and the resin usage-amount in the case of adding resin in an oil phase from the cost of an ink and printing suitability is 5-20 mass% more preferable. When the weight average molecular weight (Mw) of the resin is low and when the addition amount is small, the effect on abrasion resistance may be reduced. On the other hand, when the weight average molecular weight is too high or the addition amount of the resin is large In some cases, the solid content of the ink increases, and problems such as clogging resistance and ejection stability may occur.

The said alkyd resin is comprised from fats and oils, a polybasic acid, and a polyhydric alcohol. Examples of the fats and oils include non-drying oils having an iodine value of 80 or less, such as coconut oil, palm oil, olive oil, castor oil, rice bran oil, and cottonseed oil, or semi-drying oils, or fatty acids thereof. Dry oils such as oil and drill oil may be partially used when the iodine value of the alkyd resin is 80 or less.
Examples of the polybasic acid include saturated polybasic acids such as phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, tetrahydrophthalic acid, maleic acid, maleic anhydride, fumaric acid, and itaconic acid. And unsaturated polybasic acids such as citraconic anhydride.
Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, glycerin, trimethylolpropane, neopentyl glycol, diglycerin, triglycerin, and pentaerythritol. Slits, dipentaery slits, mannits, sorbits and the like can be mentioned. The oil length of the alkyd resin is represented by mass% in the resin when the fatty acid in the fat / oil is present as triglyceride. The alkyd resin has an oil length of preferably 60 to 90 and an iodine value of 80 or less from the viewpoint of abrasion resistance, clogging resistance, ejection stability and the like. The alkyd resin has a weight average molecular weight (Mw) of preferably less than 30,000, more preferably 10,000 or less.

-Pigment-
As the pigment contained in the oil phase or the aqueous phase, known pigments of various colors can be used, and when dispersed in carbon blacks such as acetylene black, channel black, and furnace black, particularly in the aqueous phase. Is a metal powder such as carbon black, aluminum powder, and bronze powder, which is said to be self-dispersed with the carbon black surface modified with various hydrophilic groups; inorganic pigments such as petals, yellow lead, ultramarine, chromium oxide, and titanium oxide; Phthalocyanine pigments such as metal-free phthalocyanine pigments and copper phthalocyanine pigments; azo pigments such as insoluble azo pigments, azo lake pigments, and condensed azo pigments; anthraquinone, quinacridone, isoindolinone, isoindoline, dioxazine, and selenium , Perylene, perinone, thioindigo, quinophthalone, gold Complex, condensed polycyclic pigments such as organic pigments lake pigments such as acidic or basic dyes, or fluorescent pigments, and the like. As the fluorescent pigment, when the synthetic resin is bulk polymerized or after polymerization, a fluorescent dye that develops various hues is dissolved or dyed, and the resulting colored bulk resin is pulverized and refined so-called synthetic Examples of the synthetic resin that is a resin solid solution type and that carries a dye include fluorescent pigments that carry a melamine resin, urea resin, sulfonamide resin, alkyd resin, polyvinyl chloride resin and the like on the dye. When properties such as zeta potential are close, two or more kinds of colorants may be added in the same phase.

When carbon black as the colorant is added to the oil phase, commercially available products can be used as acidic carbon black having a pH of less than 5, for example, MA-100, MA-7, MA-77, MA -11, # 40, # 44 (all manufactured by Mitsubishi Chemical Corporation), Raven 1100, Raven 1080, Raven 1255, Raven 760, Raven 410 (all manufactured by Colombian Carbon Co., Ltd.), and the like.
There is no restriction | limiting in particular in the addition amount in the emulsion ink of the said pigment, According to the objective, it can select suitably, Usually, 2-15 mass% is preferable.

  The pigment dispersant is not particularly limited as long as it does not inhibit the formation of an emulsion, and can be appropriately selected according to the purpose. For example, the nonionic surfactant for an emulsifier, an alkylamine polymer compound , Aluminum chelate compound, styrene-maleic anhydride copolymer, partial alkyl ester of polyacrylic acid, polyalkylene polyamine, aliphatic polyvalent carboxylic acid, polyether, ester type anionic surfactant, high molecular weight polycarboxylic acid Dispersion of insoluble colorants such as long chain amine salts, polyamide compounds, phosphate ester surfactants, alkyl sulfocarboxylates, α-olefin sulfonates, dioctyl sulfosuccinates, polyethyleneimines, alkylolamine salts, alkyd resins, etc. The storage stability of resin and ink If have a range ionic surfactants, amphoteric surfactants may also be used. These may be used individually by 1 type and may use 2 or more types together.

There is no restriction | limiting in particular in the addition amount of the said pigment dispersant, According to the objective, it can select suitably, 40 mass% or less of the total mass of a coloring agent is preferable, and 2-35 mass% is more preferable.
The alkyd resin is particularly effective for the dispersion stability of the insoluble colorant when a high molecular weight resin is added, but the amount of resin added when the alkyd resin is used alone or in combination with other dispersants is insoluble. 5% by mass or more of the colorant is preferable.

The gelling agent has a role of improving the storage stability, fixability, and fluidity of the ink by gelling the resin contained in the oil phase. As the gelling agent added to the ink of the present invention, A compound capable of coordinating with the above resin is preferred. Examples of such compounds are organic acid salts, organic chelate compounds, metal soap oligomers and the like containing metals such as Li, Na, K, AlCa, Co, Fe, Mn, Mg, Pb, Zn, and Zr. Specifically, octylic acid metal salts such as aluminum octylate; naphthenic acid metal salts such as manganese naphthenate; stearates such as zinc stearate; organic chelate compounds such as aluminum diisopropoxide monoethyl acetoacetate Can be mentioned.
There is no restriction | limiting in particular in the addition amount of the said gelling agent, According to the objective, it can select suitably, 15 mass% or less of the resin in an oil phase is preferable, and 5-10 mass% is more preferable.

Examples of the antioxidant added to the oil phase include dibutylhydroxytoluene, propyl gallate, and butylhydroxyanisole. These additions prevent oxidation of the binder resin or the like in the oil phase, thereby preventing an increase in the viscosity of the ink.
There is no restriction | limiting in particular in the addition amount of the said antioxidant, According to the objective, it can select suitably, 2 mass% or less is preferable with respect to the total amount of the oil phase in ink, 0.1-1.0 mass% Is more preferable.

The extender pigment is not particularly limited, and can be added to the oil phase, the aqueous phase, or both phases for preventing bleeding and adjusting the viscosity, and either inorganic fine particles or organic fine particles are preferable. Examples of the inorganic fine particles include clay, silica, talc, clay, calcium carbonate, barium sulfate, titanium oxide, alumina white, diatomaceous earth, kaolin, mica, and aluminum hydroxide. Examples of the organic fine particles include polyacrylate resin, polyurethane resin, polyester resin, polyethylene resin, polypropylene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polysiloxane resin, phenol resin, epoxy resin, or these A copolymer, and the like.
Commercially available products of the extender pigment include, for example, Aerosil 200, Aerosil R972, etc. (manufactured by Nippon Aerosil Co., Ltd.), NEW D ORBEN (manufactured by Shiroishi Kogyo Co., Ltd.), BEN-GEL, S-BEN, ORGANITE, etc. Manufactured), TIXOGEL series (VP, DS, GB, VG, EZ-100, etc.), OPTIGEL (manufactured by Nissan Gardler Catalyst), and the like.
There is no restriction | limiting in particular in the addition amount in the emulsion ink of the said extender, According to the objective, it can select suitably, 0.1-50 mass% is preferable, and 1-5 mass% is more preferable.

<Water phase>
The oil phase of the ink-jet emulsion ink contains water and a water-soluble organic solvent. If necessary, a water-soluble polymer, an O / W resin emulsion, a pigment, a pigment dispersant, an electrolyte, an antiseptic / It contains other components such as fungicides, pH adjusters and dyes.

  If it is clean, there will be no restriction | limiting in particular if it is clean, According to the objective, it can select suitably, For example, a tap water, ion-exchange water, distilled water etc. can be used.

The water-soluble organic solvent, that is, the anti-evaporating agent or the anti-freezing agent can be used together. Examples of the water-soluble organic solvent added for these purposes include glycols such as ethylene glycol, diethylene glycol, and propylene glycol; methanol, ethanol Lower saturated monohydric alcohols such as isopropanol, butanol and isobutanol; polyhydric alcohols such as 1,3-butanediol, glycerin and sorbitol;
The addition amount of the water-soluble organic solvent is preferably 15% by mass or less of the total mass of the aqueous phase in the ink, and more preferably 4 to 12% by mass.

The water-soluble polymer compound is added for humidification and thickening, and examples thereof include natural polymer compounds, semi-synthetic polymer compounds, and synthetic polymer compounds. These may be used individually by 1 type and may use 2 or more types together.
Examples of the natural polymer compound include starch, mannan, sodium alginate, galactan, tragacanth gum, gum arabic, pullulan, dextran, xanthan gum, glue, gelatin, collagen, casein and the like.
Examples of the semi-synthetic polymer compound include carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxymethyl starch, carboxymethyl starch, and dialdehyde starch.
Examples of the synthetic polymer compound include acrylic acid resin derivatives such as polyacrylic acid, sodium polyacrylate, and triethanolamine polyacrylate; synthetic polymers such as polyvinyl alcohol, polyacrylamide, polyethylene oxide, and polyvinyl methyl ether. Is mentioned.
The amount of the water-soluble polymer compound added is not particularly limited and may be appropriately selected depending on the purpose. The amount of water contained in the ink is preferably 25% by mass or less, more preferably 0.5 to 15% by mass. .

The electrolyte is added to the aqueous phase in order to enhance the storage stability of the emulsion. Therefore, it is desirable to use when no material affected by the electrolyte is present in the aqueous phase. The electrolyte used in the present invention is preferably magnesium sulfate.
As said electrolyte, you may use other electrolyte together in the range which does not inhibit storage stability etc. other than said magnesium sulfate. The electrolyte is preferably an electrolyte containing anions such as citrate ions, tartrate ions, sulfate ions, acetate ions, or alkali metal ions or alkaline earth metal ions. As the electrolyte, in addition to magnesium sulfate, sodium sulfate, sodium citrate, sodium hydrogen phosphate, sodium borate, sodium acetate, and the like are preferable.
There is no restriction | limiting in particular in the addition amount of the said electrolyte, According to the objective, it can select suitably, 0.1-2 mass% of a water phase is preferable, and 0.5-1.5 mass% is more preferable.

There is no restriction | limiting in particular as said O / W type | mold resin emulsion, Although it can select suitably from well-known things and can use it, a synthetic polymer compound or a natural polymer compound may be sufficient. Examples of the synthetic polymer compound include polyvinyl acetate resin, acrylic ester resin, methacrylic ester resin, polyvinyl chloride resin, ethylene-vinyl acetate copolymer, vinyl acetate-acrylic ester copolymer, styrene- Examples thereof include acrylic acid ester copolymers, vinylidene chloride-acrylic acid ester copolymers, vinyl chloride-vinyl acetate copolymers, and urethane resins. Examples of the natural polymer compound include a polymer compound that can be added to an oil phase that is commonly used in inkjet emulsion inks. These may be used individually by 1 type and may use 2 or more types together.
Further, the dispersion method of the oil-in-water resin emulsion is not particularly limited, and a dispersant, a protective colloid, and a surfactant may be added, or may be synthesized by soap-free emulsion polymerization. There is no restriction | limiting in particular in the minimum film forming temperature of the said oil-in-water resin emulsion, According to the objective, it can select suitably, 40 degrees C or less is preferable.

The antiseptic / antifungal agent is added to prevent bacteria and fungi from growing in the emulsion, and is effective when the emulsion is stored for a long period of time. The antiseptic / antifungal agent is not particularly limited and may be appropriately selected from known ones. Examples include salicylic acid, phenols, methyl p-oxybenzoate, ethyl p-oxybenzoate, and the like. Aromatic hydroxy compounds or chlorinated compounds thereof, sorbic acid, dehydroacetic acid and the like, and these may be used alone or in combination of two or more.
The addition amount of the antiseptic / antifungal agent is not particularly limited and may be appropriately selected depending on the purpose. It is preferably 3% by mass or less based on the total mass of water contained in the emulsion ink, 1.2 mass% is more preferable.

  As the pH adjuster added to the aqueous phase, so-called Good buffer solution is used, and when necessary, these pH adjusters can be added to keep the pH of the aqueous phase at 6-8. If the pH of the aqueous phase deviates from the above range, the pigment aggregates or the effect is impaired when a water-soluble polymer is added.

Next, the method for producing the inkjet emulsion ink of the present invention is not particularly limited and can be appropriately selected from known methods according to the purpose. For example, an oil phase and an aqueous phase liquid are prepared. Both of these may be emulsified in a known emulsifier to obtain ink. That is, oil, an emulsifier, and an oil phase in which additives such as a colorant and a resin added as necessary are well dispersed are prepared, and water, a water-soluble organic solvent, and, if necessary, added thereto. An aqueous solution in which additives such as colorants and electrolytes are well dispersed may be gradually added and emulsified. The average particle size of the insoluble colorant dispersed in the oil phase is preferably 1 to 0.01 μm, and more preferably 0.1 to 0.01 μm. The viscosity of the ink can also be adjusted depending on the stirring conditions, and is not particularly limited as long as it is a viscosity suitable for the system, and can be appropriately selected according to the purpose. The viscosity at a shear rate of 100 s ⁻¹ is 3 -40 mPa · s is preferable, and 6-20 mPa · s is more preferable.

  The ink-jet emulsion ink of the present invention is an ink-jet head that deforms a diaphragm that forms a wall surface of an ink flow path by using a piezoelectric element as pressure generating means for pressurizing ink in the ink flow path as an ink-jet head. A so-called piezo type that discharges ink droplets by changing the temperature (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 Laid-Open No. 61-59911), the diaphragm and the electrode forming the wall surface of the ink flow path are arranged to face each other, and the diaphragm is deformed by the electrostatic force generated between the diaphragm and the electrode. As a result, any ink jet type such as an electrostatic type that discharges ink droplets by changing the volume of the ink flow path (see JP-A-6-71882) can be used. It can also be used well for printers equipped with a printer.

  The ink-jet emulsion 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 system. The water-based 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 record, 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 above-described ink-jet emulsion ink of the present invention in a container, and further includes other members appropriately selected as necessary.
The container is not particularly limited, and its shape, structure, size, material and the like can be appropriately selected according to the purpose. For example, at least an ink bag formed of an aluminum laminate film, a resin film, or the like Preferred examples include those possessed.

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 10 is filled into the ink bag 41 from the ink inlet 42 and exhausted, and then the ink inlet 42 is closed by fusion. When in use, the needle of the apparatus main body is inserted into the ink discharge port 43 made of a rubber member and supplied to the apparatus.
The ink bag 41 is formed of a packaging member such as a non-permeable aluminum laminate film. As shown in FIG. 2, the ink bag 41 is usually accommodated in a plastic cartridge case 44 and is detachably mounted on various ink jet recording apparatuses.

(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 forming an image by applying a stimulus to the ink jet emulsion ink of the present invention and causing the ink jet emulsion ink to fly.
The ink flying means is means for forming an image by applying a stimulus to the inkjet emulsion ink of the present invention and causing the inkjet emulsion ink to fly. The ink flying means is not particularly limited and may be appropriately selected according to the purpose. Examples thereof include various heads (ink discharge heads), and particularly a head having a plurality of nozzle rows and a liquid storage device. It is preferable to have a sub-tank that contains the liquid supplied from the tank and supplies the liquid to the head.
The sub tank includes negative pressure generating means for generating a negative pressure in the sub tank, atmospheric release means for releasing the inside of the sub tank to the atmosphere, and detection means for detecting the presence or absence of ink based on a difference in electrical resistance. What has is preferable.

  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, a light, and the like. Specifically, for example, a piezoelectric actuator such as a piezoelectric element, Examples include thermal actuators that use phase change due to liquid film boiling using electrothermal transducers such as heating resistors, shape memory alloy actuators that use metal phase changes due to temperature changes, electrostatic actuators that use electrostatic force, etc. It is done.

  There is no particular limitation on the manner of flying the inkjet emulsion ink, and it varies depending on the type of the stimulus. For example, when the stimulus is “heat”, recording is performed on the inkjet emulsion ink in the recording head. Thermal energy corresponding to the signal is applied using, for example, a thermal head, bubbles are generated in the inkjet emulsion ink by the thermal energy, and the inkjet emulsion ink is ejected from the nozzle holes of the recording head by the pressure of the bubbles. And the like. 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 a method of ejecting and ejecting the ink-jet emulsion ink as droplets from the nozzle holes of the recording head.

  Further, it is preferable to have a scraping means for scraping off the fixed ink on the empty ejection receiver. As the scraping means, either a wiper or a cutter is preferable.

  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.

  Here, one aspect of 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 stocks an apparatus main body 1, a paper feed tray 2 for loading paper mounted on the apparatus main body 1, and paper on which an image is recorded (formed) mounted on the apparatus main body 1. A paper discharge tray 3 and an ink cartridge loading unit 6. On the upper surface of the ink cartridge loading unit 6, an operation unit 7 such as operation keys and a display is arranged. The ink cartridge loading unit 6 has a front cover 8 that can be opened and closed for attaching and detaching the ink cartridge 10.

  As shown in FIGS. 4 and 5, in the apparatus main body 1, the carriage 13 is slid in the main scanning direction by a guide rod 11 and a stay 12 which are guide members horizontally mounted on left and right side plates (not shown). It is held movably and moved and scanned in the direction of the arrow in FIG.

The carriage 13 includes a plurality of recording heads 14 including four inkjet recording heads that eject inkjet emulsion ink droplets of each color of yellow (Y), cyan (C), magenta (M), and black (Bk). The ink discharge ports are arranged in a direction crossing the main scanning direction, and are mounted with the ink droplet discharge direction facing downward.
The inkjet recording head constituting the recording head 14 includes a piezoelectric actuator such as a piezoelectric element, a thermal actuator that uses a phase change caused by liquid film boiling using an electrothermal transducer such as a heating resistor, and a metal phase caused by a temperature change. A shape memory alloy actuator that uses a change, an electrostatic actuator that uses an electrostatic force, or the like as an energy generating means for discharging an emulsion ink for inkjet can be used.
In addition, the carriage 13 is equipped with a sub tank 15 for each color for supplying ink of each color to the recording head 14. The sub-tank 15 is supplied with the ink-jet emulsion ink of the present invention from the ink cartridge 10 of the present invention loaded in the ink cartridge loading section 6 via an ink-jet emulsion ink supply tube (not shown).

  On the other hand, as a paper feeding unit for feeding the paper 22 stacked on the paper stacking unit (pressure plate) 21 of the paper feeding tray 2, a half-moon roller (feeding) that separates and feeds the paper 22 one by one from the paper stacking unit 21. A separation pad 24 made of a material having a large friction coefficient is provided opposite to the paper roller 23) and the paper feed roller 43, and the separation pad 24 is urged toward the paper feed roller 23 side.

  As a transport unit for transporting the paper 22 fed from the paper feed unit below the recording head 14, a transport belt 31 for transporting the paper 22 by electrostatic adsorption and a guide 25 from the paper feed unit. The counter roller 32 for transporting the paper 22 fed via the transport belt 31 with the transport belt 31 and the paper 22 fed substantially vertically upward are changed by about 90 ° to be copied on the transport belt 31. A conveying guide 33 and a tip pressure roller 35 urged toward the conveying belt 31 by the pressing member 34, and a charging roller 36 as a charging means for charging the surface of the conveying belt 31. It has been.

  The conveyance belt 31 is an endless belt, is stretched between the conveyance roller 37 and the tension roller 38, and can circulate in the belt conveyance direction. A guide member 77 is disposed on the back side of the conveyance belt 31 so as to correspond to a printing area by the recording head 14. As a paper discharge unit for discharging the paper 22 recorded by the recording head 14, a separation claw 51 for separating the paper 22 from the conveyance belt 31, a paper discharge roller 52, and a paper discharge roller 53 are provided. The paper discharge tray 2 is disposed below the paper discharge roller 52.

  A double-sided paper feeding unit 61 is detachably attached to the back surface of the apparatus main body 1. The double-sided paper feeding unit 61 takes in the paper 22 returned by the reverse rotation of the transport belt 31, reverses it, and feeds it again between the counter roller 32 and the transport belt 31. A manual paper feed unit 62 is provided on the upper surface of the duplex paper feed unit 61.

  In this ink jet recording apparatus, the paper 22 is separated and fed one by one from the paper feed unit, and the paper 22 fed substantially vertically upward is guided by the guide 25 and between the transport belt 31 and the counter roller 32. It is sandwiched and conveyed. Further, the front end is guided by the transport guide 33 and pressed against the transport belt 31 by the front end pressure roller 35, and the transport direction is changed by approximately 90 °.

At this time, the conveyance belt 37 is charged by the charging roller 36, and the sheet 22 is conveyed by being electrostatically attracted to the conveyance belt 31. Therefore, by driving the recording head 14 according to the image signal while moving the carriage 13, ink droplets are ejected onto the stopped paper 22 to record one line, and after the paper 22 is conveyed by a predetermined amount, Record the next line. Upon receiving a recording end signal or a signal that the trailing edge of the paper 22 has reached the recording area, the recording operation is finished and the paper 22 is discharged onto the paper discharge tray 3.
When it is detected that the remaining amount of the inkjet emulsion ink in the sub tank 15 has decreased, a required amount of the inkjet emulsion ink is supplied from the ink cartridge 10 to the sub tank 15.

  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, but the present invention can be similarly applied to a line type ink jet recording apparatus having a line type head.

  Further, the ink jet recording apparatus and the ink jet recording method of the present invention can be applied to various types of recording by the ink jet recording method. For example, the ink jet recording apparatus, the facsimile apparatus, the copying apparatus, the printer / fax / copier multifunction machine, etc. It can be particularly preferably applied.

(Ink record)
The ink recorded matter recorded by the ink jet recording apparatus and the ink jet recording method of the present invention is the ink recorded matter of the present invention. The ink recorded matter of the present invention has an image formed on the recording medium using the water-based ink of the present invention.
There is no restriction | limiting in particular as said recording medium, According to the objective, it can select suitably, For example, a plain paper, glossy paper, special paper, cloth, a film, an OHP sheet etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.
The ink recorded matter has high image quality, no bleeding, excellent temporal stability, and can be suitably used for various purposes as a material on which various prints or images are recorded.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

(Examples 1-7 and Comparative Examples 1-4)
For Examples 1 to 7 and Comparative Examples 1 and 2, water-in-oil type (= W / O) emulsion inks for inkjets were prepared with the compositions described in Tables 1 to 5 below. . The ink is a set of four colors of cyan, magenta, yellow, and black.
First, oil, a pigment, and a pigment dispersant are kneaded with three rolls (manufactured by Inoue Seisakusho, S-4 · 3/4 × 11) to prepare a pigment dispersion. Additional oil and an emulsifier are added to the pigment dispersion, and the mixture is stirred and dispersed with a dissolver (DISPERMAT-FE) to obtain an oil phase. A water phase composed of water, a water-soluble organic solvent, an antibacterial agent, and an electrolyte is added to this oil phase, emulsified with a vacuum emulsification stirrer (PVQ-3UN, manufactured by Mizuho Kogyo Co., Ltd.), and filtered using a 3 μm filter. A water-in-oil (= W / O) emulsion ink for inkjet was prepared.
In Comparative Example 3, a water-soluble dye ink having a composition shown in Table 6 below was prepared by a conventional method.
In Comparative Example 4, a water-soluble pigment ink was prepared by a conventional method with the composition shown in Table 6 below.

  Next, various characteristics of the obtained inks of Examples 1 to 7 and Comparative Examples 1 to 4 were evaluated as follows. The results are shown in Tables 1-6.

<Clogging resistance>
The clogging resistance was measured by using an ink jet printer (BJ-F850, manufactured by Canon Inc.) and Type 6200 (manufactured by Ricoh Co., Ltd.) as a print test sheet, and after printing the head position adjustment pattern, the power was turned on. Nozzle check pattern printing was performed after standing for a period of time, and the check pattern defect state was ranked in five stages to evaluate clogging resistance. In addition, it shows that clogging resistance is so favorable that a number is large.

<Discharge stability>
The discharge stability was determined by performing line printing at 0.75 points using an inkjet printer (BJ-F850, manufactured by Canon Inc.) and Type 6200 (produced by Ricoh Co., Ltd.) as a print test paper, and line loss and linearity. Were evaluated, and the discharge stability was evaluated. In addition, it shows that discharge stability is so favorable that a number is large.

<Reproducibility of fine lines (feathering)>
Fine line reproducibility (feathering) is 0.75-point line printing using an inkjet printer (BJ-F850, manufactured by Canon Inc.) and Type 6200 (manufactured by Ricoh Co., Ltd.) as a print test paper. Was left for 24 hours, the line width was measured at 5 points / 100 mm, the variation width was considered as the degree of feathering, and was ranked into five stages to evaluate fine line reproducibility (feathering). In addition, it shows that fine line reproducibility is so favorable that a number is large.

<Color reproducibility>
Color reproducibility was measured using cyan, magenta, yellow, red, green, and blue solid images using an inkjet printer (BJ-F850, manufactured by Canon Inc.) and Type 6200 (produced by Ricoh Co., Ltd.) as a printing test paper. After forming, the print sample is left for 24 hours, each color difference L ^* a ^* b ^* is measured, and the saturation C ^* is calculated by the following formula (1), and is ranked in five stages to evaluate the color reproducibility. . It can be said that the greater the saturation C ^* , the larger the color development possible range, and the better the color reproducibility. In addition, it shows that color reproducibility is so favorable that a number is large.

<Color-bleeding bleeding (color bleed)>
Color-bleeding blur (color bleed) is performed using cyan / magenta, cyan / yellow, magenta / yellow using an inkjet printer (BJ-F850, manufactured by Canon Inc.) and Type 6200 (produced by Ricoh Co., Ltd.) as a print test sheet. , Black / Cyan, Black / Magenta, Black / Yellow, solid images are formed adjacent to each other, and the print sample is left for 24 hours to observe color bleeding near the boundary, that is, color bleeding (color bleeding). Rank was divided into 5 levels, and the evaluation of blurring on the color boundary was made. In addition, it shows that a bleeding resistance is so favorable that a number is large.

<Back-through resistance>
Anti-through-through printing is performed by forming solid images of cyan, magenta, yellow, and black using an inkjet printer (BJ-F850, manufactured by Canon Inc.) and Type 6200 (produced by Ricoh Co., Ltd.) as a print test paper. The samples were allowed to stand for 24 hours, the image density on the front surface and the image density on the back surface were measured, and the image density ratio on the back surface / image density on the front surface was calculated as a percentage. The larger the number, the better the resistance to see-through.

<Handling immediately after printing>
As for handling properties immediately after printing, solid images of cyan, magenta, yellow, and black are formed using an inkjet printer (BJ-F850, manufactured by Canon Inc.) and Type 6200 (produced by Ricoh Co., Ltd.) as a printing test paper. 5 seconds later, the solid part of the print sample is rubbed with a clock meter (manufactured by Toyo Seiki Seisakusho), the image density of the friction part and the non-friction part is measured, and the friction part image density / non-friction part image density ratio is calculated as a percentage. The ranking was divided into five levels, and the handling property was evaluated immediately after printing. Those having no difference between the image density of the friction part and the image density of the non-friction part are excellent in handling properties immediately after printing. In addition, it shows that handling property is so favorable that a number is large.

<Ink storage stability>
The storage stability of the ink was hermetically sealed in a glass bottle, stored in an oven at 60 ° C., and the amount of change in viscosity after one month was ranked in five stages to evaluate the storage stability. The viscosity was measured with a tuning fork type vibration viscometer SV-10 (manufactured by A & D). In addition, it shows that the storage stability of ink is so favorable that a number is large.

<Abrasion resistance>
The rubbing resistance was determined by forming a solid image of cyan, magenta, yellow, and black using an inkjet printer (BJ-F850, manufactured by Canon Inc.) and Type 6200 (produced by Ricoh Co., Ltd.) as a print test paper. The solid part of the printed sample after time was rubbed with a clock meter (manufactured by Toyo Seiki Seisakusho), the image density of the friction part and the non-friction part was measured, and the ratio of the friction part image density / non-friction part image density was calculated as a percentage. It was classified into stages and evaluated for abrasion resistance. Those having no difference between the image density of the friction part and the image density of the non-friction part are excellent in abrasion resistance. In addition, it shows that abrasion resistance is so favorable that a number is large.

<Light resistance>
The light fastness is obtained by forming a solid image of cyan, magenta, yellow, and black using an inkjet printer (BJ-F850, manufactured by Canon Inc.) and Type 6200 (produced by Ricoh Co., Ltd.) as a printing test paper, for 24 hours. After the elapse of time, a light resistance acceleration test was conducted under the following conditions, and the degree of image deterioration before and after the test was ranked in five stages to evaluate light resistance. Those having no difference between the image density of the irradiated area and the image density of the non-irradiated area are excellent in light resistance. In addition, it shows that light resistance is so favorable that a number is large.
[Light Acceleration Test Conditions]
Using a weatherometer Ci5000 (manufactured by Atlas Co., Ltd., light source: xenon arc lamp, optical filter: inner S-type polysilicate, outer soda / lime), temperature and humidity in the tester 25 ° C / 60%, black panel temperature 40 ° C, irradiation The energy is 0.18 W / m ² and the irradiation time is 48 hours.

<Water resistance>
Water resistance was determined by using an inkjet printer (BJ-F850, manufactured by Canon Inc.) and Type 6200 (produced by Ricoh Co., Ltd.) as a print test paper, and forming a solid image of cyan, magenta, yellow, and black, 24 hours later. The print sample was immersed in ion-exchanged water for 5 seconds, and the degree of image deterioration before and after the immersion was ranked in five stages to evaluate water resistance. Those having no difference between the image density of the immersion area and the image density of the non-immersion area are excellent in water resistance. In addition, it shows that water resistance is so favorable that a number is large.

<Moisture resistance>
The moisture resistance was determined by forming a solid image of cyan, magenta, yellow, and black using an inkjet printer (BJ-F850, manufactured by Canon Inc.) and Type 6200 (produced by Ricoh Co., Ltd.) as a print test paper, and for 24 hours. Later, the print samples were stored in a temperature / humidity tester (30 ° C./90%) for 72 hours, and the degree of image deterioration before and after storage was ranked in five stages to evaluate moisture resistance. Those having no difference between the image density after storage at 30 ° C./90% and the image density before storage at 30 ° C./90% are excellent in water resistance. In addition, it shows that moisture resistance is so favorable that a number is large.

The abbreviations in Tables 1 to 6 represent the following meanings.
* C represents cyan, m represents magenta, y represents yellow, and k represents black.
* Pigment PB15: 3 is phthalocyanine blue # 15: 3 * Pigment DQ122 is dimethylquinacridone # 122 * Pigment MA74 is monoazo # 74 * Pigment acid CB is acid carbon black * Dye DB86 is direct blue No. 86 * Dye AR92 is Acid Red No. 92 * Dye DY98 is Direct Yellow No. 98 * Dye DB 168 is Direct Blue No. 168 * Resin component KG836 is a product name manufactured by Arakawa Chemical Industries, Ltd .: Rosin modified Phenol resin * Resin component KG846 is a trade name manufactured by Arakawa Chemical Industries, Ltd .: Rosin-modified phenol resin * Water-soluble organic solvent: 1,3-BD (1,3-butanediol)

なお、油成分（１）〜（４）のヨウ素価は、鉱物油であるため、無視できるほど低い。
（１）Ｓｕｎｐｅｒ１１０（サン石油株式会社製）
（２）ＡＦ６（日石三菱株式会社製）
（３）５号ソルベント（日石三菱株式会社製）
（４）ＡＦ４（日石三菱株式会社製）
（５）ＳｏｙＧｏｌｄ１０００（ＡＧ Ｅｎｖｉｒｏｎｍｅｎｔａｌ Ｐｒｏｄｕｃｔｓ ＬＬＣ） Oil components (1) to (5) in Tables 1 to 5 are as shown in Table 7 below.

In addition, since the iodine value of oil component (1)-(4) is mineral oil, it is so low that it can be disregarded.
(1) Sunper110 (manufactured by Sun Oil Co., Ltd.)
(2) AF6 (Nisseki Mitsubishi Corporation)
(3) No. 5 Solvent (Nisseki Mitsubishi Corporation)
(4) AF4 (Nisseki Mitsubishi Corporation)
(5) Soy Gold 1000 (AG Environmental Products LLC)

（１）ＮＩＫＫＯＬ ＳＯ−１０Ｖ（日光ケミカルズ株式会社製）
（２）ＮＩＫＫＯＬ ＳＯ−１５Ｖ（日光ケミカルズ株式会社製）
（３）ＮＩＫＫＯＬ ＳＯ−３０Ｖ（日光ケミカルズ株式会社製）
（４）ＮＩＫＫＯＬ ＴＯ−１０６（日光ケミカルズ株式会社製）
（５）ＮＩＫＫＯＬ ＰＲ１５（日光ケミカルズ株式会社製） The emulsifiers (1) to (5) in Tables 1 to 5 are as shown in Table 8 below.

(1) NIKKOL SO-10V (manufactured by Nikko Chemicals Co., Ltd.)
(2) NIKKOL SO-15V (manufactured by Nikko Chemicals Co., Ltd.)
(3) NIKKOL SO-30V (manufactured by Nikko Chemicals Co., Ltd.)
(4) NIKKOL TO-106 (Nikko Chemicals)
(5) NIKKOL PR15 (manufactured by Nikko Chemicals Co., Ltd.)

The ink-jet emulsion ink of the present invention is particularly preferably used in an ink-jet recording method for forming a color image on a recording medium by ejecting and flying ink as droplets from a fine ejection port. It can be widely used as ink for general writing tools, recorders, and pen plotters.
The ink jet recording apparatus and the ink jet recording method of the present invention can be applied to various types of recording by the ink jet recording method, and are widely applied to, for example, an ink jet recording printer, a facsimile apparatus, a copying apparatus, a printer / fax / copier multifunction machine, and the like. can do.

FIG. 1 is a schematic view showing an example of the ink cartridge of the present invention. FIG. 2 is a schematic view including a case (exterior) of the ink cartridge of FIG. FIG. 3 is a schematic explanatory view showing an example of the ink jet recording apparatus of the present invention. FIG. 4 is a schematic explanatory view showing an example of the internal structure of the ink jet recording apparatus of FIG. FIG. 5 is a schematic enlarged view showing an example of the inkjet head of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Apparatus main body 2 Paper feed tray 3 Paper discharge tray 6 Ink cartridge loading part 7 Operation part 8 Front cover 10 Ink cartridge 11 Guide rod 12 Stay 13 Carriage 14 Recording head 15 Sub tank 16 Supply tube 22 Paper 23 Paper feed roller 24 Separation pad 25 Guide 31 Conveying belt 32 Counter roller 33 Conveying guide 34 Holding member 36 Charging roller 37 Conveying roller 38 Tension roller 41 Ink bag 42 Ink inlet 43 Ink outlet 44 Cartridge exterior 51 Separation claw 52 Discharging roller 53 Discharging roller 61 Double-sided feeding Paper unit 62 Manual feed unit 77 Guide member

Claims (11)

Comprising an oil phase 10-90% by weight and a water phase 90 to 10 wt%, at least initial boiling point comprises a non-ionic surfactant HLB3~5 as 290 ° C. or more oil components and an emulsifier to the oil phase ,
The inkjet emulsion ink, wherein the nonionic surfactant of HLB 3 to 5 is a polyglycerin hydroxy fatty acid ester .   The inkjet ink according to claim 1, wherein the oil component is a vegetable oil-modified ester having an iodine value of 100 or less. The ink-jet emulsion ink according to claim 1, further comprising an oil-soluble resin in the oil phase. The inkjet emulsion ink according to any one of claims 1 to 3, wherein the water phase contains at least water and a water-soluble organic solvent. The inkjet emulsion ink according to any one of claims 1 to 4, comprising a pigment in at least one of the oil phase and the aqueous phase. An ink cartridge comprising the ink-jet emulsion ink according to claim 1 contained in a container. 6. An ink jet recording apparatus comprising at least ink flying means for forming an image by applying a stimulus to the ink jet emulsion ink according to claim 1 and causing the ink jet emulsion ink to fly. The inkjet recording apparatus according to claim 7, wherein the stimulus is at least one selected from heat (temperature), pressure, vibration, and light. 6. An ink jet recording method comprising at least an ink flying step of forming an image by applying a stimulus to the ink jet emulsion ink according to claim 1 and causing the ink jet emulsion ink to fly. The inkjet recording method according to claim 9, wherein the stimulus is at least one selected from heat (temperature), pressure, vibration, and light. An ink recorded matter comprising an image formed using the inkjet emulsion ink according to any one of claims 1 to 5 on a recording medium.

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