JP2017088638A - Oil-based recording liquid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an oil-based recording liquid which can improve a clear folder storage property of a record material for a long period of time.SOLUTION: An oil-based recording liquid includes a color material and an oil-based medium. As the oil-based medium, ester of dry oil fatty acid and alcohol is contained by 80 mass% or more, with the alcohol having 3 or less carbon atoms. The oil-based recording liquid further includes at least one selected from a metal soap and a metal complex. A metal included in the metal soap or the metal complex is at least one selected from Co, Mn, Pb, Zr, Ca, Ba, K and Fe.SELECTED DRAWING: None

Description

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

  Development of office-use inkjet printers is ongoing. An office use printer is required to be capable of high-speed printing with high image quality on a recording medium such as plain paper, and to be able to handle a finisher such as bookbinding after printing. For this reason, 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 for plain paper, and to prevent back-through to enable double-sided printing, Furthermore, it is required that paper deformation such as cockling and curling does not occur after high-speed printing. When an aqueous recording liquid containing 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 is unlikely to occur. Development of recording liquid is also underway.

  When a volatile organic compound is used as a medium used for the oil-based recording liquid, there is a risk of causing health damage such as allergies when the volatile organic compound is released into the environment. Therefore, a low-volatile organic compound is used as a medium used for the oil-based recording liquid. However, when printing is performed using an oil-based recording liquid that uses a low-volatile organic compound as the medium, the medium is low-volatile, so it remains inside the paper and penetrates to generate back-through or bleed. 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-based medium moves to the clear folder, so that only the inside of the clear folder expands and the clear folder faces outward. It may be deformed by curling or wavering to turn up. In particular, when a recorded matter recorded on a recording medium with a high duty is sandwiched between clear folders, the clear folder is greatly bent outward, which causes a problem in use.

  To solve this problem, 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 highly polar medium, the attack property to the clear folder is improved. Is reduced to suppress deformation (see, for example, Patent Document 1). Here, 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 as a medium.

JP 2009-275211 A

  However, if the viscosity of the recording liquid and the polarity of the medium are too high, there will be problems with the ejection characteristics of the recording liquid and sticking when the recorded material is stored repeatedly, and the deformation of the clear folder is about 10 days at the longest. It is limited to a short time and the suppression effect is not enough. 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 over a long period of time.

  Accordingly, some aspects of the present invention provide an oil-based recording liquid that can improve the clear folder storage property of recorded matter over a long period of time by solving at least a part of the above-described problems. is there.

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

[Application Example 1]
One aspect of the oil-based recording liquid according to the present invention is:
Including a coloring material and an oily medium,
The oily medium contains at least 80% by mass of a dry oil fatty acid and an alcohol ester.

  According to the oil-based recording liquid according to the application example described above, the oil medium contains 80% by mass or more of a dry oil fatty acid and an alcohol ester, thereby suppressing the deformation of the clear folder over a long period of time and maintaining the clear folder storage property for a long time. It is possible to provide an oil-based recording liquid that can be improved over a long period of time.

[Application Example 2]
In the above application example,
The alcohol may have 4 or more carbon atoms.

[Application Example 3]
In the above application example,
The alcohol has 3 or less carbon atoms,
Furthermore, at least 1 sort (s) selected from the group which consists of a metal soap and a metal complex 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,
Furthermore, a dry oil can be included.

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

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

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

  Here, the “oil-based recording liquid” in the present specification is a recording liquid mainly composed of an oil-based medium, and means a recording liquid that does not substantially contain water. Here, “substantially free of water” means that water is not intentionally added when producing the recording liquid, and a trace amount of the recording liquid inevitably mixed during production or storage. It does not matter if it contains moisture.

  The specific water content of the “oil-based recording liquid substantially free of water” is preferably such that the water content in the oil-based recording liquid is 3% by mass or less, more preferably 1% by mass or less. More preferably, it is less than 0.05% by mass, more preferably less than 0.01% by mass, still more preferably less than 0.005% by mass, and most preferably less than 0.001% by mass.

  Hereinafter, in this embodiment, an example in which an oil-based recording liquid is used as an oil-based inkjet ink composition for ink-jet recording (hereinafter also simply referred to as ink) is given, and components included in the oil-based inkjet ink composition and components that can be included Will be described.

1.1. Colorant The oil-based inkjet ink composition according to this embodiment contains a colorant. As the color material, pigments such as oily dyes, colored inorganic pigments, and colored organic pigments that are 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.

  In the case of using a pigment, particularly when 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, Without limitation, conventionally known inorganic pigments and organic pigments can be used.

  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, isoindolinones. 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, and daylight fluorescent pigments; inorganic pigments such as carbon black Etc.

  More specifically, examples of the pigment when the oil-based inkjet ink composition according to this embodiment is a magenta or red recording liquid 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.

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

  Examples of the pigment when the oil-based inkjet ink composition according to this embodiment is a green or cyan ink include C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 16, C.I. I. Pigment blue 60, C.I. I. Pigment green 7, C.I. I. And CI Pigment Green 36.

  Examples of the pigment when the oil-based inkjet ink composition according to this embodiment is a black ink include carbon black.

  Examples of the pigment 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. And CI Pigment White 21.

As a commercially available product, for example, carbon black MA11, MA100, MA220, MA600a, # 40, and # 44 manufactured by Mitsubishi Chemical are preferably cited as black pigments. Examples of pigments other than black include SYMULERBrilliant Carmine 6B, SYMULER Red, FASTOGENSuper Magenta, SYMULER Fast Yellow, and FASTOGEN Blue manufactured by Dainippon Ink, Inc.
4RO-2, FASTOGEN Green, FASTOGEN SuperViolet, etc. are mentioned. These pigments may be used alone or in appropriate combination.

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

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

  Here, the “average particle diameter” in the present specification means a 50% average particle diameter (d50) in terms of a sphere obtained by a light scattering method for ink. “50% average particle diameter in terms of sphere by light scattering method (d50)” is a value obtained as follows. The particles in the dispersion medium are irradiated with light, and the generated diffracted scattered light is measured by detectors arranged in front, side, and rear of the dispersion medium. Using the measurement value, assuming that the particles that are originally indefinite are spherical, the total volume of the particle population converted to a sphere equal to the volume of the particles is 100%, and a cumulative curve is obtained. The point at which the cumulative value becomes 50% is defined as the 50% average particle diameter (d50).

When a pigment is used as the coloring material, any dispersant used in a normal 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 the pigment is stably dispersed in the solvent. For example, Solsperse 5000, Solsperse 13940, Solsperse 11200, Solsperse 21000, Solsperse 28000 manufactured by Nippon Lubrizol are available. Etc.

  In the oil-based inkjet ink composition according to this embodiment, the content of the dispersant can be appropriately selected according to the pigment to be dispersed, but with respect to 100 parts by mass of the pigment in the oil-based inkjet ink composition. Preferably, it is 5 to 200 mass parts, More preferably, it is 30 to 120 mass parts.

  Preferable examples of commercially available dyes used in the oil-based inkjet ink composition according to this embodiment include vaLifast Black 3810, elixa Black846, OIL BLACK HBB, and OIL BLACK No. 5 manufactured by Orient Chemical. In addition, as 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 IF-YL LOW iG LOW iGLOW iGLOW iGLOW iGLOW iGLOW iGLOW iGLOW iGlWelGlS 1101 etc. are mentioned. These dyes may be used alone or in appropriate combination.

1.2. Oily medium The oil-based inkjet ink composition according to this embodiment contains an oily medium. Here, the “oil-based medium” in this specification refers to a liquid medium in which a color material such as a pigment is dispersed contains an organic solvent (organic solvent), and refers to a liquid medium at normal temperature and pressure. In addition, when the oil-based medium is an organic solvent-containing material composed of an organic solvent and a mixture other than the organic solvent, the oil-based medium indicates a material whose organic solvent content exceeds 5% by mass.

  The oil-based inkjet ink composition according to the present embodiment contains 80% by mass or more of a dry oil fatty acid and an alcohol ester as an oily medium. Since drying oil has a high viscosity, there are problems with ejection properties when used in inks for ink jet recording. However, drying oil fatty acid and alcohol esters have low viscosity and can be ejected even when used in inks for ink jet recording. There is no problem with sex. Moreover, the attack property to PP which is a material of the clear folder is low, and the oxidative polymerization of the ink is promoted by having many double bonds in the molecular structure. For this reason, by using it as the main component of the ink according to the present embodiment, even if the viscosity is low before recording, the ink after recording rapidly cures to become high viscosity, and the oily medium contained in the ink is usually used. It is fixed in a recording medium such as paper. Thereby, even if the recorded matter is sandwiched between the clear folders, the oil-based medium is suppressed from moving to the clear folder, and the clear folder storage property is improved.

  The drying oil fatty acid used as the raw material of the ester is obtained by hydrolyzing drying oil. Examples of the dry oil include linseed oil, tung oil, coconut oil, shiso oil, walnut oil, cocoon oil, safflower oil, and sunflower oil, as will be described later. The drying oil can be produced by a known method.

The alcohol used as the raw material of the ester may be an unsaturated alcohol, and can be used without limitation on the number of carbons. After recording, the ester is immediately hydrolyzed on the recording medium, and the decomposed alcohol is Since there is a possibility of shifting to a clear folder, it is necessary to adjust the recording liquid composition according to the carbon number.
When the carbon number of the alcohol is 3 or less, the alcohol tends to volatilize, and even if the alcohol in the recording medium moves to the clear folder and is deformed, it tends to return to the PP of the ester. It is more preferable that the oxidative polymerization reaction of the ink is completed before the oily medium migrates and the decomposed alcohol does not migrate to the clear folder. It is preferable to promote.

  On the other hand, when the carbon number of the alcohol is 4 or more, the attacking property of the ester to PP is low, but the decomposed alcohol is less likely to volatilize, so it is easy to move to the clear folder. It will be deformed. When the metal soap or metal complex is contained in the ink, the hydrolysis reaction of the ester is promoted. Therefore, it is preferable that the metal soap or metal complex is not contained in the ink.

  The method for producing the ester of the drying oil fatty acid and the alcohol is not particularly limited and can be produced by a known method. For example, JP 2005-53871 A, JP 2009-203343 A, and JP 2011-99009 A. It can be produced 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, more preferably 90% by mass or more, with respect to the total mass of the oil-based inkjet ink composition, from the viewpoint of ink ejection.

  Examples of the ester of drying 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, for linseed oil fatty acid 2-ethylhexyl, linolenic acid 2-ethylhexyl (SP value: 9.5, iodine value: 195) 61%, oleic acid 2-ethylhexyl (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 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 thereto, soybean oil fatty acid methyl, 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 drying oil fatty acid and alcohol ester corresponds to the fatty acid composition of the drying oil fatty acid used.

1.3. Metal Soap, Metal Complex The oil-based inkjet ink composition according to this embodiment preferably contains at least one selected from the group consisting of metal soaps and metal complexes. Metal soaps and metal complexes are also called dryers (curing accelerators) and act as oxidizing agents that promote the oxidative polymerization of organic compounds contained in the oily medium. For this reason, 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 quickly cured, and the oil-based medium contained in the ink is fixed in the recording medium. The As a result, even when the recorded matter is sandwiched between the clear folders, the oil-based medium is suppressed from moving to the clear folder, and the clear folder is prevented from being deformed.

In this 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 the raw material for the organic acid metal salt, an organic acid that has been conventionally used as a general raw material for dryers can be used without any particular limitation. Specifically, for example, an organic acid such as propionic acid, octylic acid, naphthenic acid, neodecanoic acid, tung oil acid, linseed oil acid, soybean oil acid, resin acid, etc. can be used. From the point obtained, 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.

  Among these metal-containing compounds (metal salts), for example, cobalt promotes oxidation at the interface between the ink coating and air, and other manganese is moderate and works inside as well as surface oxidation. Accelerate polymerization of Auxiliary driers such as zirconium and calcium improve overall performance in combination with the previously described driers, but have little effect when used alone.

As an organic acid metal salt used in the present embodiment, for example, the general formula (A)
(OMR) Formula 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.)
The organic acid metal salt represented by these is mentioned.

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

  As described above, in this embodiment, cobalt drier and manganese drier can be used as the metal soap and metal complex, but it is preferable to use a manganese drier from the viewpoint of the use environment. In addition, since manganese is inferior in activity to cobalt, when a manganese dryer is used, it is preferably used together with a ligand that activates the manganese dryer. Examples of the ligand include 2,2′-bipyridine, 2- (aminomethyl) pyridine, 2-hydroxymethylpyridine, and the like. A ligand can be used individually by 1 type or in mixture of 2 or more types.

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

  Examples of organic acid metal salts used as other dryers include organic acid cobalt boron metal salts and organic acid manganese boron metal salts. These may be used singly or in combination, but when used together, they are excellent in the drying property of the coating film with a thick film that is difficult to be uniformly cured, so that the combined use is preferable. Furthermore, when the organic acid cobalt boron metal salt and the organic acid manganese boron metal salt are used in combination with the organic acid manganese boron metal salt, the combined use of the organic acid cobalt boron metal salt and the organic acid manganese boron metal salt is preferable because the coating film is excellent in dryness. In addition, when the organic acid cobalt boron metal salt and the organic acid manganese metal salt are used in combination, a low-cost dryer excellent in drying acceleration effect can be obtained, and the combined use 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 JP-B-63-63551. .

  In addition, it is preferable from the viewpoint of easy handling and uniform mixing that these organic acid metal salts are previously diluted with an organic solvent before being added to the oil-based inkjet ink composition. The diluted organic solvent is not 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 and cyclohexanol; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; propyl ether, methyl cellosolve, cellosolve, butyl cellosolve, methylcarbitol, Ether solvents such as butyl carbitol can be used, and these may be used alone or in combination of two or more.

1.4. Dry oil In the oil-based inkjet ink composition according to this embodiment, the oil-based medium preferably contains a dry oil. Dry oil has a high viscosity, so if it is used in many inks for ink jet recording, there will be a problem in ejection properties. However, the attack property of PP, which is a material of clear folder, is low, and the ink has many double bonds. The oxidative polymerization of is promoted. For this reason, by using supplementarily in the ink according to the present embodiment, the ink after recording is quickly cured, and the oily medium contained in the ink is fixed in the recording medium. Thereby, even if the recorded matter is sandwiched between the clear folders, the oily medium is suppressed from moving to the clear folder, and the clear folder storage property is improved.

  Here, the dry oil refers to an oil having an iodine value of 130 or more, and examples thereof include linseed oil, tung oil, coconut oil, shiso oil, walnut oil, coconut oil, safflower oil, and sunflower oil. These drying oils can be used alone or in combination of two or more.

  When a dry 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 ejection.

1.5. Other Oil-Based Medium The oil-based inkjet ink composition according to the present embodiment can further contain various known vegetable oils and / or petroleum-based solvents other than the above-mentioned dry oil fatty acid and alcohol ester as the oil-based medium, and is nonpolar. Both organic solvents and polar organic solvents can be used.

1.5.1. Nonpolar organic solvent Examples of the nonpolar organic solvent used in the oil-based inkjet ink composition according to the embodiment include hydrocarbon solvents such as naphthenic, paraffinic, and isoparaffinic solvents, fluorine-based surfactants, and silicon-based interfaces. Examples include activators. As these nonpolar organic solvents, commercially available ones may be used, for example, aliphatic saturated hydrocarbons such as dodecane, Expar Mobil Isopar, Exsol, JX Nippon Oil & Energy Corporation AF solvent. Normal paraffin H, AS Sol manufactured by Wilvie Co., Ltd., Dust Clean manufactured by Matsumura Oil Co., Ltd., Sansen manufactured by Sun Oil Co., Ltd., the same sampler, 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 this 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, 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 acid, ethyl oleate, isopropyl oleate, butyl oleate, hexyl oleate, methyl linoleate, isobutyl linoleate, ethyl linoleate, butyl stearate, hexyl stearate, isotearic acid Octyl, 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, such as higher alcohols such as isomyristyl alcohol, isopalmityl alcohol, isostearyl alcohol, and oleyl alcohol. .

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

  Examples of the fatty acid solvent include fatty acids having 4 or more carbon atoms in one molecule, preferably 9 to 22 carbon atoms in one molecule. For example, isononanoic acid, isomyristic acid, hexadecanoic acid, 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, 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, with respect to the total mass (100% by mass) of the ink composition.

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

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

  The organic solvent has low PP attack and also has a double bond to promote oxidative polymerization of the ink. For this reason, when used in the ink according to the present embodiment, the ink after recording is quickly 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 remaining solvent is prevented from moving to the clear folder, and the clear folder storage property is improved.

  Examples of the organic solvent include linolenic acid monoglyceride (SP value 10.3, iodine value 216), and a compound represented by the general formula (2) (SP value 12.6, iodine value 297). And compounds represented by the above general formula (3) (SP value 11.5, iodine value 231). These can be used individually by 1 type or in mixture of 2 or more types.

1.5.4. Allyl Compound The oil-based inkjet ink composition according to this embodiment can contain an allyl compound as an oil-based medium. Allyl compounds tend to undergo a crosslinking reaction at the α-carbon position. For this reason, when an allyl compound is included as a component of the oily medium, oxidative polymerization of the ink is promoted on the recording medium after recording. For this reason, by using the ink according to the present embodiment, even if the viscosity is low before recording, the ink after recording rapidly cures to become high viscosity, and the oil-based medium contained in the ink is contained in the recording medium. Fixed. As a result, even if the recorded matter is sandwiched between the clear folders, the oil-based medium is suppressed from moving to the clear folder, and the clear folder storage property is improved.

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

  Among allyl compounds, from the viewpoint of reactivity, allyl ether is preferable, and a compound represented by the following general formula (1) is 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. R ⁴ represents H, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 8 carbon atoms.

  As the allyl compound, among the compounds represented by the general formula (1), the SP value is 9.5 or more, and the iodine value is 120 or more. The allyl compound is represented by the following general formulas (2) and (3). A compound is preferred.

  Commercially available products of the compound represented by the above general formula (2) (SP value 12.6, iodine value 297) and the compound represented by the above 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 Corporation) can also be used.

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

1.6. Other Components The oil-based inkjet ink composition according to this embodiment may further include other additives contained in a normal oil-based inkjet ink composition. Examples of other additives include stabilizers such as antioxidants and ultraviolet absorbers, and binder resins.

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

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

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

1.7. Method for Producing Oil-Based Inkjet Ink Composition The oil-based inkjet ink composition according to this embodiment can be produced by a known conventional method. In the case of using a pigment as a colorant, first, a pigment, a dispersant, and an organic solvent (partial) 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 characteristics. Subsequently, an organic solvent (remaining amount) and other additives (for example, a surfactant or 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 this embodiment preferably has a surface tension at 20 ° C. of 20 mN / m or more and 50 mN / m from the viewpoint of the balance between recording quality and reliability as an inkjet ink composition. 25 mN / m or more and 40 mN / m or less is more preferable. The surface tension is measured by using an automatic surface tension meter CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.) by confirming the surface tension when the platinum plate is wetted with ink in an environment of 20 ° C. be able to.

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

1.9. Applications The oil-based inkjet ink composition according to this embodiment is stored in an ink cartridge of a known inkjet recording apparatus, ejects ink droplets, and attaches the droplets to a recording medium such as paper to record an image. . The ink jet recording apparatus is preferably an ink jet recording apparatus that is equipped with an electrostrictive element that can vibrate based on an electrical signal and that can eject ink by the vibration of the electrostrictive element. The oil-based inkjet ink composition according to the present embodiment contains 80% by mass or more of a dry oil fatty acid and an alcohol ester as an oily medium, so that no problem occurs in ink ejection, and an image can be recorded. . Further, in the recorded matter obtained using the oil-based inkjet ink composition according to the present embodiment, the clear folder is prevented from being deformed by the influence of the oil-based medium in the obtained image.

  As described above, according to the oil-based inkjet ink composition according to the present embodiment, the oil folder contains 80% by mass or more of a dry oil fatty acid and an alcohol ester, so that a clear folder by a recorded matter using this ink. It is possible to suppress the deformation of for a long 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 oil-based recording liquid compositions In Examples 1 to 12 and Comparative Example 1, each material was mixed and stirred so as to have the composition (mass%) shown in Table 1 below, and completely dissolved, and then a membrane having a pore size of 1 µm. Each oil-based ink composition was obtained by filtering with a filter. Then, the following clear folder deformation | transformation evaluation test was done about each oil-based recording liquid composition.

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

  In Example 14, 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 ink of Example 14 was produced in the same manner except for the other conditions.

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

2.2. Clear Folder Deformation Evaluation Test Each oil-based recording liquid composition obtained was filled into an ink cartridge of a remodeled ink jet printer PX-M7050F (manufactured by Seiko Epson Corporation), and solid-printed on double-sided plain plain paper (manufactured by Seiko Epson Corporation). (Rectangle 20 cm × 28 cn) was applied, and the printed matter was inserted into a clear folder made of PP. Set the clear folder with the printed material into it at 23 ° C / 50% R. H. It was left to stand in the environment for 30 days. Thereafter, the amount of the clear folder that had been left stationary was measured using a ruler, and the value was evaluated as the amount of deformation. The evaluation results were 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 oil-based recording liquid composition obtained was filled into an ink cartridge of a remodeled machine of an ink jet printer PX-M7050F (manufactured by Seiko Epson Corporation), and a test pattern including characters and 1-dot ruled lines (vertical and horizontal) (A4) 1000 sheets were continuously printed, and the quality was visually evaluated. The evaluation results were 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 drying oil fatty acid and the alcohol ester, the amount of deformation was small. In Examples 5 and 6 including Mn dryer in addition to the ester of drying oil fatty acid and alcohol, and Examples 7 to 9 including further drying oil, the amount of deformation is further reduced, and both Mn dryer and drying oil are used. In Examples 10 and 11 including the deformation, the amount of deformation was suppressed to less than 10 mm, and the clear folder storage property was improved. The content of the ester of the drying oil fatty acid and the alcohol is low, the carbon number of the alcohol constituting the ester is 4 or more, and Example 12 including Mn dryer is more dry than other examples. Even if oil was included, the amount of deformation was large, but it was not problematic for use. Also, in Examples 13 and 14 using a pigment as a color material, the same effects as in other examples using a dye as a color material were 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 number of carbon atoms of the alcohol constituting the ester is 4 or more, and in Comparative Example 1 including the Mn dryer, the drying oil is used. Even if included, the amount of deformation was large and the clear folder storage property was poor.

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

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

Claims (6)

Including a coloring material and an oily medium,
An oily recording liquid comprising 80% by mass or more of a dry oil fatty acid and an alcohol ester as the oily medium.   The oil-based recording liquid according to claim 1, wherein the alcohol has 4 or more carbon atoms. The alcohol has 3 or less carbon atoms,
The oil-based recording liquid according to claim 1, further comprising at least one selected from the group consisting of metal soaps and metal complexes.   The oil-based recording liquid according to claim 3, wherein the metal contained in the metal soap or the metal complex is at least one selected from the group consisting of Co, Mn, Pb, Zr, Ca, Ba, K, and Fe. .   The oil-based recording liquid according to any one of claims 1 to 4, further comprising a dry oil.   The oil-based recording liquid according to any one of claims 1 to 5, wherein the oil-based recording liquid is for inkjet recording.