JP6693088B2 - Oil-based inkjet ink - Google Patents

Description

  The present invention relates to an oil-based recording liquid.

  Inkjet printers for office use are being developed. Office-use printers are required to be capable of high-speed printing with high image quality on recording media such as plain paper, and to be capable of finishing such as bookbinding after printing. Therefore, as a characteristic required for the recording liquid used in this printer, it is possible to secure a high print density at a high speed with respect to plain paper, and strike-through is suppressed to enable double-sided printing, Further, it is required that paper deformation such as cockling and curling does not occur after high speed printing. When an aqueous recording liquid mixed with an aqueous medium is used as the recording liquid, paper deformation such as cockling and curling may occur after high-speed printing on plain paper, so paper deformation does not easily occur. The development of recording liquid is also in progress.

  When a volatile organic compound is used as a medium used for the oil-based recording liquid, when the volatile organic compound is released into the environment, it may cause a health hazard such as allergy. Therefore, a low-volatile organic compound is used as a medium for the oil-based recording liquid. However, when printing with an oil-based recording liquid that uses a low-volatile organic compound as the medium, the medium remains low inside the paper due to its low volatility, and the ink penetrates to cause strike-through and bleeding. The print density may be further reduced. Also, when a recording medium printed with an oil-based recording liquid is sandwiched between clear folders made of polypropylene (PP), the oil medium moves to the clear folders and only the inside of the clear folders expands, and the clear folders face outward. There is a case where it warps like curling up, or it is deformed by waving. In particular, when a recording material recorded with a high duty on a recording medium is sandwiched between clear folders, the clear folders are largely warped outward, which causes a problem in use.

  Therefore, with respect to such problems, the viscosity of the recording liquid is increased to limit the transfer of the oily medium from the recording medium to the clear folder, and by selecting a medium having a high polarity, the attack property to the clear folder is improved. Has been performed to suppress deformation (see, for example, Patent Document 1). Here, as the medium, a diester of a polyhydric alcohol and a branched aliphatic carboxylic acid or a diester of a branched aliphatic alcohol and a high aliphatic carboxylic acid is used.

JP, 2009-275211, A

  However, if the viscosity of the recording liquid or the polarity of the medium is too high, problems may occur in ejectability of the recording liquid, sticking when the recording materials are stacked and stored, and suppression of deformation of the clear folder is about 10 days at the longest. Limited for a short period of time, the suppressive effect is not sufficient. As described above, it is difficult to suppress the deformation of the clear folder due to the recorded matter using the oil-based recording liquid for a long period of time.

  Therefore, some aspects of the present invention provide an oil-based recording liquid capable of improving the clear folder storability of a recorded matter for a long period of time by solving at least a part of the above problems. is there.

  The present invention has been made to solve at least a part of the above problems, and can be realized as the following aspects or application examples.

[Application example 1]
One aspect of the oil-based recording liquid according to the present invention is
Including a colorant and an oil medium,
The oily medium contains 80% by mass or more of an ester of a dry oil fatty acid and an alcohol.

  According to the oil-based recording liquid according to the above application example, by containing 80% by mass or more of an ester of a dry oil fatty acid and an alcohol as an oil-based medium, deformation of the clear folder is suppressed for a long period of time, and the clear folder storability is maintained for a long time. It is possible to provide an oil-based recording liquid that can be improved over the entire range.

[Application example 2]
In the above application example,
The carbon number of the alcohol may be 4 or more.

[Application example 3]
In the above application example,
The alcohol has 3 or less carbon atoms,
Furthermore, at least one selected from the group consisting of metal soaps and metal complexes can be included.

[Application example 4]
In the above application example,
The metal contained in the metal soap or the metal complex may be at least one selected from the group consisting of Co, Mn, Pb, Zr, Ca, Ba, K and Fe.

[Application example 5]
In the above application example,
Further, a drying oil can be included.

[Application example 6]
In the above application example,
The oil-based recording liquid may be for inkjet recording.

  A preferred embodiment of the present invention will be described below. The embodiment described below describes an example of the present invention. Further, the present invention is not limited to the following embodiments, and includes various modifications that are carried out without changing the gist of the present invention.

1. Oil-Based Recording Liquid The oil-based recording liquid according to the present embodiment is characterized by containing a coloring material and an oil medium, and containing 80% by mass or more of a dry oil fatty acid and an ester of alcohol as the oil medium. The oil-based recording liquid according to the present invention can be used without particular limitation as an oil-based recording liquid containing a coloring material and an oil-based medium as an oil paint, a paint, a writing instrument such as a fountain pen, or a recording liquid for printing.

  Here, the "oil-based recording liquid" in the present specification is a recording liquid containing an oily medium as a main component and means a recording liquid containing substantially no water. Here, "substantially free of water" means that water is not intentionally added when the recording liquid is produced, and a trace amount of the recording liquid inevitably mixed during the production or storage of the recording liquid. It may contain water.

  The specific water content of the "substantially water-free oil-based recording liquid" is preferably 3% by mass or less, more preferably 1% by mass or less, in the oil-based recording liquid. And more preferably less than 0.05% by mass, more preferably less than 0.01% by mass, even more preferably less than 0.005% by mass, and most preferably less than 0.001% by mass.

  Hereinafter, in the present embodiment, an example in which the oil-based recording liquid is used as an oil-based inkjet ink composition for inkjet recording (hereinafter, also simply referred to as ink) will be given, and components contained in the oil-based inkjet ink composition and components that may be contained therein. Will be described.

1.1. Color Material The oil-based inkjet ink composition according to the present embodiment contains a color material. As the coloring material, an oily dye or a pigment such as a colored inorganic pigment or a colored organic pigment that is usually used in conventional oil-based inkjet ink compositions can be used. These coloring materials may be used alone or in combination of two or more.

  When a pigment is used, if the average particle diameter of the pigment dispersion in the recording liquid is 20 nm or more and 200 nm or less and the hue is black, yellow, magenta, cyan, red, green, blue or orange, Conventionally known inorganic pigments and organic pigments can be used without limitation.

  Examples of such pigments include azo pigments such as azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments; phthalocyanine pigments, perylene and perylene pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, thioindigo pigments, isoindolinone. Polycyclic pigments such as pigments and quinophthalone pigments; dye lakes such as basic dye type lakes and acid dye type lakes; organic pigments such as nitro pigments, nitroso pigments, aniline black, daylight fluorescent pigments; inorganic pigments such as carbon black Etc.

  More specifically, when the oil-based inkjet ink composition according to the present embodiment is used as a magenta or red recording liquid, examples of pigments include C.I. I. Pigment Red 2, C.I. I. Pigment Red 3, C.I. I. Pigment Red 5, C.I. I. Pigment Red 6, C.I. I. Pigment Red 7, C.I. I. Pigment Red 15, C.I. I. Pigment Red 16, C.I. I. Pigment Red 48: 1, C.I. I. Pigment Red 53: 1, C.I. I. Pigment Red 57: 1, C.I. I. Pigment Red 122, C.I. I. Pigment Red 123, C.I. I. Pigment Red 139, C.I. I. Pigment Red 144, C.I. I. Pigment Red 149, C.I. I. Pigment Red 166, C.I. I. Pigment Red 170, C.I. I. Pigment Red 177, C.I. I. Pigment Red 178, C.I. I. Pigment Red 194, C.I. I. Pigment Red 209, C.I. I. Pigment Red 222, C.I. I. Pigment Red 224, C.I. I. Pigment Violet 19 and the like.

When the oil-based inkjet ink composition according to the present embodiment is used as an orange or yellow recording liquid, examples of pigments include C.I. I. Pigment Orange 31, C.I. I. Pigment Orange 43, C.I. I. Pigment Orange 64, C.I. I. Pigment Yellow 12, C.I. I. Pigment Yellow 13, C.I. I. Pigment Yellow 14, C.I. I. Pigment Yellow 15, C.I. I. Pigment Yellow 17, C.I. I. Pigment Yellow 74, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 94, C.I. I. Pigment Yellow 128, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 180 and the like.

  When the oil-based inkjet ink composition according to this embodiment is a green or cyan ink, examples of pigments include C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15: 2, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 16, C.I. I. Pigment Blue 60, C.I. I. Pigment Green 7, C.I. I. Pigment Green 36 and the like.

  When the oil-based inkjet ink composition according to the present embodiment is used as a black ink, examples of the pigment include carbon black.

  Examples of the pigment used when the oil-based inkjet ink composition according to this embodiment is a white ink include C.I. I. Pigment White 6, C.I. I. Pigment White 18, C.I. I. Pigment White 21 and the like.

As commercially available products, as black pigments, for example, carbon blacks MA11, MA100, MA220, MA600a, # 40 and # 44 manufactured by Mitsubishi Chemical are preferred. Examples of pigments other than black include SYMULER Brilliant Carmine 6B, SYMULER Red, FASTOGEN Super Magenta, SYMULER Fast Yellow, FASTOGEN Blue manufactured by Dainippon Ink.
4RO-2, FASTOGEN Green, FASTOGEN SuperViolet and the like. These pigments may be used alone or in an appropriate combination.

  The content of the pigment in the oil-based inkjet ink composition according to the present embodiment can be appropriately selected depending on the application and printing characteristics, but since the excellent hiding property and color reproducibility are obtained, the total mass of the ink (100 Mass%), preferably 0.01 mass% or more and 20 mass% or less, more preferably 0.5 mass% or more and 15 mass% or less, particularly preferably 1 mass% or more and 10 mass% or less. % Or less.

  As described above, the average particle diameter of the pigment is preferably 20 nm or more and 200 nm or less. When the average particle diameter is 20 nm or more, the color developability becomes better, and the ink is easy to use as an inkjet ink. On the other hand, when the average particle diameter is 200 nm or less, it becomes easy to use in the inkjet system. In addition, when the oil-based recording liquid is used as the inkjet recording liquid, the average particle diameter is more preferably 50 nm or more and 150 nm or less because it is excellent in storage stability, ejection stability, and sedimentation property.

  Here, the “average particle diameter” in the present specification means a sphere-converted 50% average particle diameter (d50) obtained by a light scattering method for ink. The “sphere-converted 50% average particle diameter (d50) by light scattering method” is a value obtained as follows. The particles in the dispersion medium are irradiated with light, and the diffracted and scattered light generated is measured by the detectors arranged in front of, in the side of, and behind the dispersion medium. Using the measured values, the particles which are originally indefinite are assumed to be spherical, and the cumulative volume of the particle group converted into a sphere equal to the volume of the particles is calculated as 100% to obtain a cumulative curve. The point at which the cumulative value at that time is 50% is the 50% average particle diameter (d50).

When a pigment is used as the coloring material, any dispersant used in a usual oil-based inkjet ink composition can be used from the viewpoint of improving the dispersion stability of the pigment in the oil-based inkjet ink composition. The pigment dispersant that can be used in the present invention is not particularly limited as long as it can stably disperse a pigment in a solvent. For example, Nippon Lubrizol Solsperse 5000, Solsperse 13940, Solsperse 11200, Solsperse 21000, Solsperse 28000. Etc.

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

  Preferable examples of commercially available dyes used in the oil-based inkjet ink composition according to the present embodiment include vaLifast Black 3810, elixa Black 846, OIL BLACK HBB, and OIL BLACK No. 5 manufactured by Orient Chemical Co., Ltd. Further, for dyes other than black, OIL BLUE 2N, elixa Orange-240, VALIFAST BLUE 1603, elixa Green-502, VALIFAST ORANGE 1201, OIL GREEN 530, elixa Green 29-540, OIL YELLOWAWEL, WILA-IELAWEL, GLEA-ELAWEL, GLA-ELAWEL, LOWAYELWEL, GLA-ELAWEL. 1101 and the like. These dyes may be used alone or in combination as appropriate.

1.2. Oily Medium The oily inkjet ink composition according to the present embodiment contains an oily medium. Here, the “oil-based medium” in the present specification refers to a liquid medium in which a coloring material such as a pigment is dispersed and containing an organic solvent (organic solvent), and refers to a liquid medium at room temperature and atmospheric pressure. In the case where the oily medium contains an organic solvent containing an organic solvent and a mixture other than the organic solvent, the content of the organic solvent exceeds 5% by mass.

  The oil-based inkjet ink composition according to this embodiment contains 80% by mass or more of an ester of a drying oil fatty acid and an alcohol as an oil medium. Drying oil has a high viscosity, so if it is used in many inks for ink jet recording, it causes a problem in dischargeability. However, the ester of a drying oil fatty acid and alcohol has low viscosity, and even if it is used in many inks for ink jet recording, it is discharged. There is no problem with sex. In addition, the oxidative polymerization of the ink is promoted because it has a low attack property to PP which is a material of the clear folder and has many double bonds in the molecular structure. Therefore, by using the ink as the main component of the ink according to the present embodiment, even if the viscosity is low before recording, the ink after recording quickly hardens to have high viscosity, and the oily medium contained in the ink is usually It is fixed in a recording medium such as paper. As a result, even if the recorded matter is sandwiched between the clear folders, the transfer of the oily medium to the clear folders is suppressed, and the storability of the clear folders is improved.

  The dry oil fatty acid, which is a raw material of the ester, is obtained by hydrolyzing the dry oil. Examples of the drying oil include flaxseed oil, tung oil, mustard oil, shiso oil, walnut oil, citrus oil, safflower oil, sunflower oil, and the like, as described below. The drying oil can be hydrolyzed by a known method.

The alcohol used as the raw material of the ester may be an unsaturated alcohol, and can be used without any limitation in the number of carbon atoms, but after recording, the ester is immediately hydrolyzed on the recording medium, and the decomposed alcohol is Since there is a possibility of transfer to a clear folder, it is necessary to adjust the composition of the recording liquid according to the carbon number.
When the carbon number of the alcohol is 3 or less, the alcohol easily volatilizes, and even if the alcohol in the recording medium moves to a clear folder and is deformed, it tends to return to the original state. It is more preferable that the oxidative polymerization reaction of the ink is completed before the transfer of the oily medium and the decomposed alcohol does not transfer to the clear folder, because it has a strong attack property and is used in combination with a metal soap or a metal complex described later to cure. It is preferable to promote it.

  On the other hand, when the number of carbon atoms in the alcohol is 4 or more, the ester is less attacked on PP, but the decomposed alcohol is less likely to volatilize, and thus it is easier to move to a clear folder, which is a clear folder. It will transform. If the ink contains a metal soap or a metal complex, the hydrolysis reaction of the ester is promoted. Therefore, it is preferable that the ink contains no metal soap or a metal complex.

  The method for producing an ester of a dry oil fatty acid and an alcohol is not particularly limited and can be produced by a known method. For example, JP-A-2005-53871, JP-A-2009-203343, and JP-A-2011-99009 are available. It can be manufactured by the method described in the publication.

  The content of the ester of the dry oil fatty acid and the alcohol is 80% by mass or more, and more preferably 90% by mass or more, based on the total mass of the oil-based inkjet ink composition, from the viewpoint of ink ejection properties.

  Examples of the ester of dry oil fatty acid and alcohol include linseed oil fatty acid 2-ethylhexyl and linseed oil fatty acid methyl ester. As an example of the composition of each ester, in linseed oil fatty acid 2-ethylhexyl, 2-ethylhexyl linolenate (SP value: 9.5, iodine value: 195) 61%, 2-ethylhexyl oleate (SP value: 8. 6, iodine value: 64) 14%, 2-ethylhexyl linoleate (SP value: 8.5, iodine value: 129) 15%, 2-ethylhexyl palmitate (SP value: 8.5, iodine value: 0) 7 %, 2-ethylhexyl stearate (SP value: 8.5, iodine value: 0) 3%, and in linseed oil fatty acid methyl ester, methyl linolenate (SP value: 9.6, iodine value: 267) 61% , Methyl oleate (SP value: 8.6, iodine value: 94) 14%, methyl linoleate (SP value: 8.6, iodine value: 189) 15%, methyl palmitate SP value: 8.6, iodine value: 0) 7%, methyl stearate (SP value: 8.6, iodine value: 0) 3%, but not limited to, soybean oil fatty acid methyl ester, soybean oil Fatty acid isobutyl, tall oil fatty acid methyl, tall oil fatty acid isobutyl and the like can also be used. Thus, the composition of the ester of the dry oil fatty acid and the alcohol corresponds to the fatty acid composition of the dry oil fatty acid used.

1.3. Metal Soap, Metal Complex The oil-based inkjet ink composition according to the present embodiment preferably contains at least one selected from the group consisting of metal soap and metal complexes. The metal soap and the metal complex are also called a drier (curing accelerator), and act as an oxidant that accelerates the oxidative polymerization of the organic compound contained in the oily medium. Therefore, when recording on a recording medium such as paper using the oil-based inkjet ink composition according to the present embodiment, the ink after recording is rapidly cured, and the oil-based medium contained in the ink is fixed in the recording medium. It As a result, even if the recorded matter is sandwiched between the clear folders, the oil medium is prevented from moving to the clear folders, and the clear folders are prevented from being deformed.

In the present embodiment, the metal contained in the metal soap or metal complex is Co (cobalt), Mn (manganese), Pb (lead), Zr (zirconium), Ca (calcium), Ba (barium), K (potassium). And at least one selected from the group consisting of Fe (iron). In this embodiment, the metal soap or metal complex is an organic acid metal salt. As the organic acid used as a raw material for the organic acid metal salt, an organic acid conventionally used as a general raw material for a dryer can be used without particular limitation. Specifically, for example, propionic acid, octylic acid, naphthenic acid, neodecanoic acid, tung oil acid, flaxseed oil acid, soybean oil acid, it is possible to use an organic acid such as a resin acid, excellent drying promoting effect From the viewpoint of obtaining, it is preferable to use an aliphatic monocarboxylic acid having 3 to 12 carbon atoms, and it is more preferable to use octylic acid, naphthenic acid, or neodecanoic acid. These may be used alone or in combination of two or more.

  Of the compounds (metal salts) containing these metals, cobalt, for example, promotes oxidation at the interface between the ink coating and the air, and other manganese, etc., are moderate and act on the inside as well as on the surface. Accelerate the polymerization of. Auxiliary driers such as zirconium and calcium improve the overall performance in combination with the previously mentioned driers, but have little effect on their own.

Examples of the organic acid metal salt used in the present embodiment include those represented by the general formula (A)
(OMR) Type ₃ (A)
(In the formula, M represents a cobalt atom or a manganese atom, R represents an organic acid group, and three Rs in the molecule may be the same or different.)
An organic acid metal salt represented by

  In the general formula (A), the organic acid group R is a carboxylate group of an organic acid such as propionic acid, octylic acid, naphthenic acid, neodecanoic acid, tung oil, flaxseed oil, soybean oil, and resin acid. It is preferably a carboxylate group of an aliphatic monocarboxylic acid having 3 to 12 carbon atoms, and more preferably a carboxylate group of octylic acid, naphthenic acid or neodecanoic acid.

  As described above, in the present embodiment, the metal soap and the metal complex include a cobalt drier and a manganese drier, but it is preferable to use the manganese drier from the viewpoint of use environment. Since manganese has a lower activity than cobalt, when a manganese drier is used, it is preferably used together with a ligand that activates the manganese drier. Examples of the ligand include 2,2′-bipyridine, 2- (aminomethyl) pyridine, 2-hydroxymethylpyridine and the like. The ligand may be used alone or in combination of two or more.

  It is preferable to use manganese neodecanoate as the manganese dryer, and examples of commercially available products include DICATE Mn 6.5% SB manufactured by DIC Corporation.

  Other organic acid metal salts used as a dryer include organic acid cobalt boron metal salts and organic acid manganese boron metal salts. These may be used alone or in combination, but when they are used in combination, they are excellent in the drying property of a coating film in a thick film that is difficult to uniformly cure, and therefore their combination is preferable. Further, when the organic acid cobalt boron metal salt and the organic acid manganese boron metal salt are used in combination, the dryness of the coating film in a thick film is similarly excellent, and thus the combination thereof is preferable. Further, when the organic acid cobalt boron metal salt and the organic acid manganese metal salt are used in combination, a low-cost dryer having an excellent drying promoting effect can be obtained, so that the combination thereof is particularly preferable.

  The method for producing the organic acid metal salt used in the present invention is not particularly limited and can be produced by a known method. For example, it can be produced by the method described in Japanese Patent Publication No. 63-63551. ..

  Further, it is preferable to dilute these organic acid metal salts with an organic solvent in advance before adding them to the oil-based inkjet ink composition, from the viewpoint of easy handling and uniform mixing. The diluting organic solvent is not particularly limited as long as it can uniformly dissolve the organic acid metal salt, and is inert to the organic acid metal salt, for example, toluene, xylene, heptane, hexane, cyclohexane, Hydrocarbon solvents such as mineral spirits; alcohol solvents such as methanol, ethanol, propanol, cyclohexanol; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; propyl ether, methyl cellosolve, cellosolve, butyl cellosolve, methyl carbitol, An ether solvent such as butyl carbitol can be used, and these may be used alone or in combination of two or more kinds.

1.4. Dry Oil In the oil-based inkjet ink composition according to this embodiment, the oil medium preferably contains a dry oil. Since drying oil has a high viscosity, it causes a problem in dischargeability when used in many inks for inkjet recording. However, since PP, which is a material for the clear folder, has low attack property and has many double bonds, The oxidative polymerization of is promoted. Therefore, by supplementarily using the ink according to the present embodiment, the ink after recording is rapidly cured, and the oily medium contained in the ink is fixed in the recording medium. As a result, even if the recorded matter is sandwiched between the clear folders, the transfer of the oily medium to the clear folders is suppressed, and the storability of the clear folders is improved.

  Here, the drying oil refers to an oil having an iodine value of 130 or more, and examples thereof include flaxseed oil, tung oil, mustard oil, perilla oil, walnut oil, spoiled oil, safflower oil, sunflower oil, and the like. These drying oils may be used alone or in combination of two or more.

  When the drying oil is contained, the content thereof is preferably 0.05% by mass or more and 10% by mass or less with respect to the total mass of the oil-based inkjet ink composition, from the viewpoint of ink ejectability.

1.5. Other Oily Medium The oily inkjet ink composition according to the present embodiment may further include, as an oily medium, various known vegetable oils and / or petroleum-based solvents other than the esters of the dry oil fatty acid and alcohol, and the non-polar medium. Both organic solvents and polar organic solvents can be used.

1.5.1. Non-polar organic solvent Examples of the non-polar organic solvent used in the oil-based inkjet ink composition according to the present embodiment include naphthene-based, paraffin-based, isoparaffin-based hydrocarbon solvents, fluorine-based surfactants, and silicon-based interfaces. Activator etc. are mentioned. As these non-polar organic solvents, commercially available ones may be used, for example, aliphatic saturated hydrocarbons such as dodecane, ExxonMobil's Isopar, Exxol, and JX Nikko Nisseki Energy's AF solvent. , Normal Paraffin H, AS Sol manufactured by Wilvie Co., Dust Clean manufactured by Matsumura Oil Co., Ltd., Sun Sen manufactured by Sun Oil Co., Ltd., Sun Samp, Surflon manufactured by AGC Seimi Chemical Co., Ltd., and the like.

1.5.2. Polar Organic Solvent Examples of the polar organic solvent used in the oil-based inkjet ink composition according to the present embodiment include ester solvents, alcohol solvents, amide solvents, fatty acid solvents, ether solvents and the like.

  Examples of the ester solvent include higher fatty acid esters having 5 or more carbon atoms in one molecule, preferably 9 or more carbon atoms in one molecule, and more preferably 12 to 32 carbon atoms in one molecule. , For example, isodecyl isononanoate, isotridecyl isononanoate, isononyl isononanoate, methyl laurate, isopropyl laurate, isopropyl myristate, isopropyl palmitate, isooctyl palmitate, hexyl palmitate, isostearyl palmitate, isooctyl isopalmitate, olein. Methyl acidate, ethyl oleate, isopropyl oleate, butyl oleate, hexyl oleate, methyl linoleate, isobutyl linoleate, ethyl linoleate, butyl stearate, hexyl stearate, isostearate Butyl, isopropyl isostearate, 2-octyldodecyl pivalate, diisopropyl adipate, diisopropyl sebacate, diethyl sebacate, propylene glycol monocaprylate, trimethylolpropane tri-2-ethylhexanoate, glyceryl tri-2-ethylhexanoate, etc. Can be mentioned.

  Examples of the alcohol solvent include aliphatic higher alcohols having 12 or more carbon atoms in one molecule, and examples thereof include higher alcohols such as isomyristyl alcohol, isopalmityl alcohol, isostearyl alcohol, and oleyl alcohol. ..

  Examples of the amide-based solvent include acetamide, dimethylacetamide, N-methylpyrrolidinone and the like.

  Examples of the fatty acid-based solvent include fatty acids having 4 or more carbon atoms in one molecule, preferably 9 or more and 22 or less carbon atoms in one molecule, and examples thereof include isononanoic acid, isomyristic acid, hexadecanoic acid, and isopalmitin. Acid, oleic acid, isostearic acid and the like can be mentioned.

  Examples of the ether solvent include glycol ethers such as diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, and propylene glycol dibutyl ether, and acetates of glycol ethers.

  The content of these other oily media is preferably 15% by mass or less, and more preferably 10% by mass or less, based on the total mass (100% by mass) of the ink composition.

1.5.3. Organic solvent having a high SP value and a high iodine value Further, as the other oily medium, an organic solvent having an SP value of 9.5 or more and an iodine value of 120 or more may be contained. In this case, the upper limit values of the SP value and the iodine value are not particularly limited.

  Here, the SP value is a solubility parameter and is obtained, for example, by the calculation method of Fedors described in “Paint Research No. 152 (2010) P.43”. The iodine value is, for example, a value calculated according to the method specified in “JIS K 3331: 2009, hydrogenated oil / fatty acid for industrial use”.

  The above organic solvent has a low PP attack property and has a double bond to accelerate the oxidative polymerization of the ink. Therefore, when used in the ink according to the present embodiment, the ink after recording is rapidly cured, and the oily medium contained in the ink is fixed in the recording medium. As a result, even if the recorded matter is sandwiched between the clear folders, the residual solvent is prevented from transferring to the clear folders, and the storability of the clear folders is improved.

  Examples of the organic solvent include linolenic acid monoglyceride (SP value 10.3, iodine value 216), and the compound represented by the general formula (2) (SP value 12.6, iodine value 297). Also included are compounds represented by the above general formula (3) (SP value 11.5, iodine value 231). These may be used alone or in combination of two or more.

1.5.4. Allyl Compound The oil-based inkjet ink composition according to this embodiment may include an allyl compound as an oil medium. The allyl compound is likely to undergo a crosslinking reaction at the α carbon position. Therefore, when an allyl compound is contained as a component of the oily medium, the oxidative polymerization of the ink is promoted on the recording medium after recording. Therefore, by using the ink according to the present embodiment, even if the viscosity is low before recording, the ink after recording is rapidly cured to have high viscosity, and the oily medium contained in the ink remains in the recording medium. It is fixed. As a result, even if the recorded matter is sandwiched between the clear folders, the transfer of the oily medium to the clear folders is suppressed, and the storability of the clear folders is improved.

  The allyl compound can be used without particular limitation, but a compound having a high oxidative polymerization reactivity and a low PP attack property is preferable.

  Among allyl compounds, from the viewpoint of reactivity, allyl ethers are preferable, and compounds represented by the following general formula (1) are preferable.

In formula (1), R ¹ represents a methyl group or —OCH ₂ CHCH ₂ , R ² and R ³ each independently represent — (CH ₂ ) _n CHCHR ⁴ , and n is an integer of 1 or more and 20 or less. And R ⁴ represents H, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 8 carbon atoms.

  Among the compounds represented by the above general formula (1), the allyl compound is represented by the following general formulas (2) and (3) having an SP value of 9.5 or more and an iodine value of 120 or more. It is preferably a compound.

  As a commercially available product of the compound represented by the general formula (2) (SP value 12.6, iodine value 297) and the compound represented by the general formula (3) (SP value 11.5, iodine value 231) For example, Neoallyl (registered trademark) P-30 or Neoallyl (registered trademark) T-20 (manufactured by Daiso Co., Ltd.) can also be used.

  The above allyl compounds may be used alone or in combination of two or more.

1.6. Other Components The oil-based inkjet ink composition according to the present embodiment may further contain other additives contained in ordinary oil-based inkjet ink compositions. Examples of other additives include stabilizers such as antioxidants and ultraviolet absorbers, binder resins, and the like.

  Examples of the antioxidant include BHA (2,3-butyl-4-oxyanisole) and BHT (2,6-di-t-butyl-p-cresol).

  Examples of the ultraviolet absorber include benzophenone compounds and benzotriazole compounds.

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

1.7. Method for producing oil-based inkjet ink composition The oil-based inkjet ink composition according to the present embodiment can be produced by a known conventional method. When a pigment is used as a coloring material, first, a pigment, a dispersant, and an organic solvent (a part) are mixed, and then a pigment dispersion is prepared by a ball mill, a bead mill, an ultrasonic wave, a jet mill or the like, Adjust to have ink properties. Subsequently, the organic solvent (residual amount) and other additives (for example, a surfactant and a binder resin) can be added with stirring to obtain an oil-based inkjet ink composition.

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

  From the same viewpoint, the viscosity of the oil-based inkjet ink composition according to this embodiment at 20 ° C. is preferably 2 mPa · s or more and 30 mPa · s or less, and more preferably 2 mPa · s or more and 20 mPa · s or less. More preferable. The viscosity is measured by using a viscoelasticity tester MCR-300 (manufactured by Physica), increasing the Shear Rate to 10 to 1000 under an environment of 20 ° C., and reading the viscosity at Shear Rate 200. Can be measured.

1.9. Use The oil-based inkjet ink composition according to the present embodiment is contained in an ink cartridge of a known inkjet recording device, ejects ink droplets, and deposits the droplets on a recording medium such as paper to record an image. .. As the ink jet recording apparatus, an ink jet recording apparatus which is equipped with an electrostrictive element capable of vibrating based on an electric signal and configured to eject ink by vibration of the electrostrictive element is preferable. The oil-based inkjet ink composition according to this embodiment contains 80% by mass or more of an ester of a dry oil fatty acid and an alcohol as an oil medium, so that it is possible to record an image without causing a problem in ink ejection. .. Further, in the recorded matter obtained by using the oil-based inkjet ink composition according to the present embodiment, the clear folder is suppressed from being deformed due to the influence of the oil-based medium in the obtained image.

  As described above, the oil-based inkjet ink composition according to the present embodiment contains 80% by mass or more of an ester of a drying oil fatty acid and an alcohol as an oil medium, so that a clear folder by a recorded matter using this ink Can be suppressed for a long period of time.

2. EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Experimental Examples and Comparative Examples, but the present invention is not limited to these Examples.

2.1. Preparation of Oily Recording Liquid Compositions In Examples 1 to 12 and Comparative Example 1, each material was mixed and stirred to completely dissolve it so that the compositions (% by mass) shown in Table 1 below were obtained, and then a membrane having a pore size of 1 μm was used. Each oil-based ink composition was obtained by filtering with a filter. Then, the following clear folder deformation evaluation test was performed for each oil-based recording liquid composition.

  In Example 13, a solvent: 3: 5000 g, flaxseed oil: 100 g, a coloring material: 2,500 g, and a dispersant: 300 g were put in a 10 L stainless steel container and stirred for 1 hour with a dissolver manufactured by Inoue Seisakusho to manufacture a mill base. The same mill base was subjected to a 5-pass dispersion treatment in a pass operation with a Star Mill LMZ manufactured by Ashizawa Finetech Co., Ltd. (peripheral speed 12 m / s, beads used: zirconia φ0.1 mm, bead filling rate: 85%). Then, it was subjected to a centrifugal separation treatment with a cooling centrifuge (CR7N) manufactured by Hitachi Koki Co., Ltd. at an acceleration of 11000 G for 20 minutes, and then filtered with a 3 μm filter. 4100 g of Solvent 3 was added to the filtrate and sufficiently stirred to obtain an oil-based ink composition of Example 13.

  Example 14 was the same as the ink of Example 14 except that the color material 2 was changed to the color material 3 in the method for producing the oil-based ink of Example 13 and the other conditions were the same.

The materials listed in Table 1 are as follows.
-Solvent 1: Flaxseed oil fatty acid butyl-Solvent 2: Tung oil fatty acid methyl-Solvent 3: Flaxseed oil fatty acid 2-ethylhexyl-Solvent 4: Flaxseed oil fatty acid propyl-Solvent 5: Soybean oil fatty acid methyl-Mn dryer: DIC Corporation, Manganese neodecanoate-Drying oil: Kaneda Co., paulownia oil-Coloring material 1: BASF Co., Neozapon Blue 807
Color material 2: Cinquasia Magenta D4550J (manufactured by BASF)
Color material 3: Heliogen Blue D7088 (manufactured by BASF)
Dispersant: Solsperse 13940

2.2. Clear Folder Deformation Evaluation Test Each of the obtained oil-based recording liquid compositions was filled in an ink cartridge of an inkjet printer PX-M7050F (manufactured by Seiko Epson Co., Ltd.) remodeling machine, and solid printing was performed on both-side plain paper (manufactured by Seiko Epson Co., Ltd.). (Rectangle 20 cm × 28 cn) was applied and the printed matter was inserted into a PP clear folder. Place the clear folder with the printed matter in it at 23 ° C / 50% R.S. H. It was left standing sideways in the environment for 30 days. Then, the amount of the outwardly warped clear folder was measured using a ruler, and the value was evaluated as the amount of deformation. The evaluation results are ranked as follows.
5: Deformation amount less than 10 mm 4: Deformation amount 10 mm or more and less than 30 mm 3: Deformation amount 30 mm or more and less than 50 mm 2: Deformation amount 50 mm or more and less than 150 mm 1: Deformation amount 150 mm or more

2.3. Evaluation of ejection stability Each of the obtained oil-based recording liquid compositions was filled in an ink cartridge of a modified printer of the inkjet printer PX-M7050F (manufactured by Seiko Epson Corporation), and a test pattern including characters and 1-dot ruled lines (vertical, horizontal) (A4) 1000 sheets were continuously printed, and the quality was visually evaluated. The evaluation results are ranked as follows.
5: Defect rate less than 0.1% 4: Defect rate 0.1% or more and less than 1% 3: Defect rate 1% or more and less than 5% 2: Defect rate 5% or more and less than 10% 1: Defect rate 10% or more

2.4. Evaluation Results The above evaluation results are shown in the first and second rows from the bottom of Table 1. In Examples 1 to 4 containing 80% by mass or more of the ester of the dry oil fatty acid and the alcohol, the deformation amount was small. In addition to the ester of the drying oil fatty acid and the alcohol, Examples 5 and 6 further containing a Mn dryer, and Examples 7 to 9 further containing a drying oil, the amount of deformation is further reduced, and both the Mn dryer and the drying oil are further added. In Examples 10 and 11 including the above, the deformation amount was suppressed to less than 10 mm, and the storability of the clear folder was improved. The content of the ester of the dry oil fatty acid and the alcohol was low, the carbon number of the alcohol constituting the ester was 4 or more, and Example 12 including the Mn dryer was dry compared with the other Examples. Even if it contained oil, the amount of deformation was large, but there was no problem in using it. Further, in Examples 13 and 14 in which the pigment was used as the coloring material, the same effect as in the other Examples in which the dye was used as the coloring material was observed. On the other hand, the content of the ester of the drying oil fatty acid and the alcohol is 80% by mass or less, the alcohol constituting the ester has 4 or more carbon atoms, and in Comparative Example 1 including the Mn dryer, the drying oil is Even if it was included, the amount of deformation was large, and the storability of the clear folder was poor.

  As described above, according to the present embodiment, by including 80% by mass or more of the ester of the dry oil fatty acid and the alcohol as the oil medium, the deformation of the clear folder can be dramatically suppressed, and further, the Mn dryer. It is possible to suppress the deformation of the clear folder due to the recorded matter using the oil-based recording liquid for a long period of time by adding or dry oil.

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

Claims (7)

Including a colorant and an oil medium,
Examples oily medium, viewed contains a drying oil fatty acid and alcohol ester 80 wt% or more,
An oil-based inkjet ink in which the alcohol has 4 or more carbon atoms . Contains a colorant, an oily medium, and manganese neodecanoate ,
Examples oily medium, viewed contains a drying oil fatty acid and alcohol ester 80 wt% or more,
An oil-based inkjet ink in which the alcohol has 3 or less carbon atoms . The oil-based inkjet ink according to claim 2, further comprising a ligand of manganese neodecanoate. The oil-based inkjet ink according to claim 3, wherein the ligand includes at least one of 2,2'-bipyridine, 2- (aminomethyl) pyridine, and 2-hydroxymethylpyridine. The oil-based inkjet ink according to any one of claims 1 to 4, further comprising a drying oil. The oil-based inkjet ink according to any one of claims 1 to 5, further comprising an allyl compound as the oil-based medium . The oil-based inkjet ink according to claim 1, further comprising an organic solvent having an SP value of 9.5 or more and an iodine value of 120 or more as the oily medium .