JP6809054B2 - Oil-based recording liquid - Google Patents

Description

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

Development of an inkjet printer for office use is underway. Printers for office use are required to be capable of high-quality, high-speed printing on recording media such as plain paper, and to be capable of handling finishers such as bookbinding after printing. For this reason, the characteristics required for the recording liquid used in this printer are that a high print density can be secured at high speed for plain paper and that strike-through is suppressed to enable double-sided printing. Further, it is required that paper deformation such as cock ring and curl does not occur after high-speed printing. When an aqueous recording solution containing an aqueous medium is used as the ink, paper deformation such as cock ring and curl may occur after high-speed printing on plain paper, so paper deformation is unlikely to occur. Oil-based recording containing an oil-based medium. Liquid development is also underway.

When a volatile organic compound is used as an oil medium used in an oil-based recording solution, there is a risk of causing health hazards 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 solution that uses a low-volatile organic compound as the medium, the medium remains low-volatile and permeates into the recording medium, causing strike-through and bleeding. The print density may decrease from the initial stage of printing. Further, when a recording medium printed using an oil-based recording solution is sandwiched between polypropylene (PP) clear folders, 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 wavy as if it were turned up. In particular, when a recorded object recorded with a high duty on a recording medium is sandwiched between clear folders, there is a problem that the clear folder is greatly warped outward and hinders its use.

Therefore, in response to such problems, the viscosity of the recording liquid is increased to limit the solvent transfer from the recording medium to the clear folder, and by selecting a highly polar oil-based medium, the attack property to the clear folder is improved. Deformation is suppressed by reducing the amount (see, for example, Patent Document 1). Here, as the medium, a diester of a polyhydric alcohol and a branched-chain aliphatic carboxylic acid or a diester of a branched-chain aliphatic alcohol and a high-aliphatic carboxylic acid is used.

JP-A-2009-275211

However, if the viscosity of the recording liquid or the polarity of the medium is too high, problems may occur in the ejection property of the recording liquid and sticking when the recorded materials are stacked and stored, and the deformation of the clear folder can be suppressed for about 10 days at the longest. Limited to a short period of time, the inhibitory effect is not sufficient. As described above, it is difficult to suppress the deformation of the clear folder due to the recorded material 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 storage property of a recorded material for a long period of time by solving at least a part of the above-mentioned 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 solution according to the present invention is
Including coloring material and oil-based medium,
The oily medium contains a first organic solvent having an SP value of 9.5 or more and an iodine value of 120 or more.
The content of the first organic solvent is 50% by mass or more.

According to the above application example, the oil-based medium SP value is 9.5 or more, and the content of the first organic solvent having an iodine value of 120 or more is 50% by mass or more, so that the viscosity is low before recording. However, the ink after recording is rapidly cured to have a high viscosity, and the oil-based medium contained in the ink is immobilized in the recording medium. This makes it possible to provide an oil-based recording liquid capable of suppressing deformation of the clear folder for a long period of time and improving the storage property of the clear folder for a long period of time.

[Application example 2]
Another aspect of the oil-based recording solution according to the present invention is
Including coloring material and oil-based medium,
The oily medium is characterized by containing an allyl compound.

According to the above application example, since the oil-based medium contains an allyl compound, the ink after recording is rapidly cured to a high viscosity even if the viscosity is low before recording, and the oil-based medium contained in the ink is recorded. It is immobilized in the medium. This makes it possible to provide an oil-based recording liquid capable of suppressing deformation of the clear folder for a long period of time and improving the storage property of the clear folder for a long period of time.

[Application example 3]
In the above application example
The content of the second organic solvent having an SP value of 9.0 or less and an iodine value of 100 or less can be 30% by mass or less.

According to the above application example, when the SP value is 9.0 or less and the content of the second organic solvent having an iodine value of 100 or less is 30% by mass or less, the curing of the ink after recording is further promoted. Will be done. Therefore, even if the recorded material is sandwiched between the clear folders, it is possible to provide an oil-based recording liquid in which the oil-based medium is suppressed from migrating to the clear folder and the clear folder storage property is improved.

[Application example 4]
In the above application example
Furthermore, at least one selected from the group consisting of metal soaps and metal complexes can be included.

According to the above application example, since the metal soap and the metal complex act as an oxidant that promotes the oxidative polymerization of the organic compound contained in the oily medium, the curing of the ink after recording is promoted. This makes it possible to provide an oil-based recording liquid in which the oil-based medium contained in the ink is quickly fixed in the recording medium and the clear folder storage property is improved.

[Application example 5]
In the above application example
The metal contained in the metal soap or the metal complex can be at least one selected from the group consisting of Co, Mn, Pb, Zr, Ca, Ba, K and Fe.

According to the above application example, the inclusion of the metal further promotes the oxidative polymerization of the organic compound contained in the oily medium, and further promotes the curing of the ink after recording. This makes it possible to provide an oil-based recording liquid in which the oil-based medium contained in the ink is quickly fixed in the recording medium and the clear folder storage property is improved.

[Application example 6]
In the above application example
Further, drying oil can be included.

According to the above application example, the inclusion of the drying oil promotes the oxidative polymerization of the ink, and the curing of the ink after recording is promoted and fixed. As a result, even if the recorded material is sandwiched between the clear folders, it is possible to provide an oil-based recording liquid in which the residual solvent is suppressed from being transferred to the clear folder and the storage property of the clear folder is improved.

（式（１）中、Ｒ^１、Ｒ^２は、各々独立して炭素数１以上３以下のアルキル鎖を表し、Ｘｎは水素、水酸基、炭素数１以上６以下のアルキル基、炭素数１以上３以下のアルキロール基、又は式（２）で表されるアリルアルコキシアルキル基を表す。ｍは１〜３の整数を表し、ｎは、ｍ＋ｎ＝４を満たす整数を表す。式（２）中、Ｒ^３、Ｒ^４は、各々独立して炭素数１以上３以下のアルキル鎖を表す。） [Application 7]
In the above application example
The allyl compound can be a compound represented by the following formula (1).

(In the formula (1), R ¹ and R ² each independently represent an alkyl chain having 1 or more carbon atoms and 3 or less carbon atoms, and Xn is hydrogen, a hydroxyl group, an alkyl group having 1 or more carbon atoms and 6 or less carbon atoms, and 1 or more carbon atoms. It represents an alkylol group of 3 or less, or an allylalkoxyalkyl group represented by the formula (2). M represents an integer of 1 to 3, and n represents an integer satisfying m + n = 4. In the formula (2). , R ³ and R ⁴ each independently represent an alkyl chain having 1 to 3 carbon atoms.)

According to the above application example, when the allyl compound is a compound represented by the formula (1), the reactivity is further improved and the curing of the ink is promoted, and the oil-based medium contained in the ink is contained in the recording medium. It is fixed with. As a result, it is possible to provide an oil-based recording liquid having improved storage stability in a clear folder.

[Application Example 8]
In the above application example
The oil-based recording liquid can be used for inkjet recording.

According to the above application example, it can be suitably used as a recording liquid for inkjet recording.
Even if the obtained recorded material is sandwiched between clear folders, it is possible to provide an oil-based recording liquid for inkjet recording in which residual solvent is suppressed from being transferred to the clear folder and the storage property of the clear folder is improved.

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

1. 1. Oil-based recording liquid The oil-based recording liquid according to the present embodiment contains a coloring material and an oil-based medium, and the oil-based recording medium contains a first organic solvent having an SP value of 9.5 or more and an iodine value of 120 or more. The content of the first organic solvent is 50% by mass or more, or the oily medium contains an allyl compound. 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 an ink for printing.

Here, the “oil-based recording liquid” in the present specification means a recording liquid containing an oil-based medium as a main component and substantially does not contain water. In addition, "substantially water-free" means that water is not intentionally added during the production of the recording liquid, and a small amount of water inevitably mixed during the production or storage of the recording liquid. May be included.

The specific water content of the "substantially water-free oil-based recording solution" is preferably that the water content in the oil-based recording solution is 3% by mass or less, and more preferably 1% by mass or less. It means that it is more preferably less than 0.05% by mass, further 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 can be contained thereof will be given. 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, pigments such as oil-based dyes, colored inorganic pigments, and colored organic pigments 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, especially when the average particle size 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, and chelate azo pigments; phthalocyanine pigments, perylene and perylene pigments, anthraquinone pigments, quinacridone pigments, dioxandine pigments, thioindigo pigments, and isoindolinones. Polycyclic pigments such as pigments and quinophthalone pigments; dye lakes such as basic dye type rakes and acidic dye type rakes; organic pigments such as nitro pigments, nitroso pigments, aniline blacks and daylight fluorescent pigments; inorganic pigments such as carbon black And so on.

More specifically, as a pigment when the oil-based inkjet ink composition according to the present embodiment is used as a magenta or red recording liquid, for example, 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, etc.

Examples of the pigment when the oil-based inkjet ink composition according to the present 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. Pigment Yellow 180 and the like.

Examples of the pigment when the oil-based inkjet ink composition according to the present embodiment is a green or cyan recording liquid 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.

Examples of the pigment when the oil-based inkjet ink composition according to the present embodiment is used as a black recording liquid include carbon black and the like.

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

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

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 excellent hiding power and color reproducibility can be obtained, the total mass of the ink (100). It is preferably contained in the range of 0.01% by mass or more and 20% by mass or less, more preferably 0.5% by mass or more and 15% by mass or less, and particularly preferably 1% by mass or more and 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 development property becomes better, so that it becomes easy to use as an inkjet recording liquid. On the other hand, when the average particle size is 200 nm or less, it becomes easy to use in the inkjet method. Further, the average particle size is more preferably 50 nm or more and 150 nm or less because the oil-based recording liquid is excellent in storage stability, discharge stability, and sedimentation property when used as an inkjet recording liquid.

Here, the "average particle size" in the present specification means a sphere-equivalent 50% average particle size (d50) obtained by a light scattering method with respect to ink. The “sphere-equivalent 50% average particle diameter (d50) by the light scattering method” is a value obtained as follows. The particles in the oil-based medium are irradiated with light, and the diffracted scattered light generated by the detectors arranged in front, side, and rear of the oil-based medium is measured. Using the measured values, it is assumed that the particles that are originally amorphous are spherical, and the cumulative curve is obtained by assuming that the total volume of the particle population converted into a sphere equal to the volume of the particles is 100%. The point at which the cumulative value is 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 it stably disperses the pigment in the solvent. For example, Solsparse 5000, Solsparse 13940, Solspers 11200, Solspers 21000, Solspers 28000 manufactured by Japan Lubrizol. And so on.

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, but with respect to 100 parts by mass of the pigment content in the oil-based inkjet ink composition. It is preferably 5 parts by mass or more and 200 parts by mass or less, and more preferably 30 parts by mass or more and 120 parts by mass or less.

As commercially available products of the dye used in the oil-based inkjet ink composition according to the present embodiment, for example, Orient Chemical's vaLifest Black 3810, elixa Black 846, OIL BLACK HBB, OIL BLACK No. 5 and the like are preferably mentioned. 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-540, elixa Green-540, OIL YELLOWELLOW 1101 and the like can be mentioned. These dyes may be used alone or in combination as appropriate.

1.2. Oil-based medium The oil-based inkjet ink composition according to the present embodiment contains an oil-based 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, which contains an organic solvent (organic solvent), and is a liquid medium at normal temperature and pressure. 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 content of the organic solvent exceeds 5% by mass.

As the oil-based medium used in the oil-based inkjet ink composition according to the present embodiment, any of various known vegetable oils and / or petroleum-based solvents can be used, and either a non-polar organic solvent or a polar organic solvent can be used. Can also be used. Hereinafter, the oil-based medium contained in the oil-based inkjet ink composition according to the present embodiment will be described in more detail.

1.2.1. First Organic Solvent In a preferred embodiment of the present invention, the oil-based medium contains a first organic solvent having an SP value of 9.5 or more and an iodine value of 120 or more, and contains the first organic solvent. The amount is 50% by mass or more.

The content of the oil-based medium in the oil-based inkjet ink composition according to the present embodiment is 50% by mass or more, preferably 70% by mass or more, based on the total mass (100% by mass) of the ink composition. More preferably, it is 80% by mass or more.

Here, the SP value is a dissolution parameter (solubility parameter), and is obtained by, for example, the method for calculating 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, industrial hydrogenated oil / fatty acid".

The first organic solvent having an SP value of 9.5 or more and an iodine value of 120 or more has a high SP value and therefore has a low PP attack property, and also contains a large number of double bonds in its molecular structure. Oxidative polymerization of ink is fast. Therefore, when used in the ink according to the present embodiment, the ink after recording is rapidly cured, and the oil-based medium contained in the ink is immobilized in the recording medium. As a result, even if the recorded material is sandwiched between the clear folders, it is possible to provide an oil-based recording liquid in which the oil-based medium is suppressed from migrating to the clear folder and the storage property of the clear folder is improved.

In the first organic solvent, the upper limits of the SP value and the iodine value are not particularly limited. The first organic solvent includes, for example, an allyl compound having an SP value of 9.5 or more and an iodine value of 120 or more, and an unsaturated fatty acid having an SP value of 9.5 or more and an iodine value of 120 or more. Examples thereof include esters of dry oil fatty acids and alcohols.

1.2.1.1. Allyl compound Examples of the allyl compound having an SP value of 9.5 or more and an iodine value of 120 or more include a compound represented by the following formula (3).

In formula (3), R ⁵ represents a methyl group or −OCH ₂ CHCH ₂ , R ⁶ and R ⁷ each independently represent − (CH ₂ ) _n CHCHR ⁸ , and n is an integer of 1 or more and 20 or less. R ⁸ represents H, an alkyl group having 1 or more and 8 or less carbon atoms, or an aryl group having 6 or more and 8 or less carbon atoms.

The "alkyl group having 1 or more and 8 or less carbon atoms" in R ⁸ can be a linear or branched alkyl group, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or n-. Butyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, n-hexyl group, isohexyl group, sec-hexyl group, n-heptyl group, isoheptyl group, sec-heptyl Examples thereof include a group, a tert-heptyl group, an n-octyl group, an isooctyl group, a sec-octyl group, a tert-octyl group and a dimethylhexyl group. Examples of the aryl group having "6 to 8 carbon atoms" include a phenyl group, a tolyl group, and a xsilyl group.

The allyl compound having an SP value of 9.5 or more and an iodine value of 120 or more is a compound represented by the following formulas (4) and (5) among the compounds represented by the above formula (3). Is preferable.

As commercially available products of the compound represented by the above formula (4) (SP value 12.6, iodine value 297) and the compound represented by the above formula (5) (SP value 11.5, iodine value 231), for example. , Neoallyl (registered trademark) P-30 and Neoallyl (registered trademark) T-20 (manufactured by Osaka Soda Co., Ltd.) can also be used.

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

1.2.1.2. Esters of Drying Oil Fatty Acids and Alcohols Esters of drying oil fatty acids and alcohols have low viscosities, and even if they are widely used in inks for inkjet recording, there is no problem in ejection properties. In addition, PP, which is a material of the clear folder, has low attack property and has many double bonds, so that oxidative polymerization of ink is promoted. Therefore, by using the oil-based recording liquid according to the present embodiment as an oil-based medium, the ink after recording is rapidly cured to a high viscosity even if the viscosity is low before recording, and the oil-based medium contained in the ink. Is fixed in the recording medium. As a result, even if the recorded material is sandwiched between the clear folders, the oil-based medium is suppressed from migrating to the clear folder, and the oil-based recording liquid having improved storeability in the clear folder can be provided.

The ester of the drying oil fatty acid and the alcohol can be used without particular limitation as long as the SP value is 9.5 or more and the iodine value is 120 or more. The drying oil fatty acid used as a raw material for the ester is obtained by hydrolyzing the drying oil. Examples of the dry oil include flaxseed oil, tung oil, mustard oil, shiso oil, walnut oil, perilla oil, red flower oil, and sunflower oil, as described later. As a method for hydrolyzing the drying oil, it 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 in the number of carbon atoms. However, after recording, the ester is immediately hydrolyzed on the recording medium, and the decomposed alcohol is produced. May move to clear folder. Here, when the carbon number of the alcohol is 3 or less, the alcohol tends to volatilize, and even if the residual solvent in the recorded material is transferred to the clear folder and deformed, it tends to return to the original state. However, since it is preferable that the oxidative polymerization reaction of the ink is completed before the solvent is transferred and the decomposed alcohol is not transferred to the clear folder, it is preferable to use it in combination with a metal soap or a metal complex described later to promote curing.

On the other hand, when the number of carbon atoms of the alcohol is 4 or more, the decomposed alcohol is hard to volatilize, so that it is easy to move to the clear folder. When the ink contains a metal soap or a metal complex, the hydrolysis reaction of the ester described above is promoted. Therefore, it is preferable that the ink does not contain the metal soap or the metal complex.

The method for producing the dry oil fatty acid ester 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 It can be manufactured by the methods described.

When an ester of a drying oil fatty acid and an alcohol is used, the content thereof is 80% by mass or more, more preferably 90% by mass, based on the total mass of the oil-based inkjet ink composition from the viewpoint of ink ejection property. % Or more.

Examples of the ester of the drying oil fatty acid and the 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 flaxseed 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 flaxseed 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) Valuation: 0) 7%, methyl stearate (SP value: 8.6, iodine value: 0) 3%, but not limited to this. As described above, the composition of the ester of the drying oil fatty acid and the alcohol corresponds to the fatty acid composition of the drying oil fatty acid used.

1.2.2. Allyl compound As a preferred embodiment of the present invention, as described above, the oil-based medium contains a first organic solvent having an SP value of 9.5 or more and an iodine value of 120 or more, and this first organic. In addition to the example in which the content of the solvent is 50% by mass or more, there is an example in which the allyl compound is contained as the oily medium. In this case, the SP value does not necessarily have to be 9.5 or more and the iodine value does not have to be 120 or more, depending on the high reactivity of the allyl compound.

The allyl compound tends to undergo a cross-linking reaction at the α carbon position. Therefore, when the allyl compound is contained as the oil-based medium, 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 a high viscosity, and the oil-based medium contained in the ink is contained in the recording medium. It is fixed. As a result, even if the recorded material is sandwiched between the clear folders, the oil-based medium is suppressed from migrating to the clear folder, and the oil-based recording liquid with improved storability in the clear folder can be provided.

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

Among allyl compounds, from the viewpoint of reactivity, allyl ether is preferable, and the compound represented by the following formula (1) is preferable.

（式（１）中、Ｒ^１、Ｒ^２は、各々独立して炭素数１以上３以下のアルキル鎖を表し、Ｘｎは水素、水酸基、炭素数１以上６以下のアルキル基、炭素数１以上３以下のアルキロール基、又は式（２）で表されるアリルアルコキシアルキル基を表す。ｍは１〜３の整数を表し、ｎは、ｍ＋ｎ＝４を満たす整数を表す。式（２）中、Ｒ^３、Ｒ^４は、各々独立して炭素数１以上３以下のアルキル鎖を表す。）

(In the formula (1), R ¹ and R ² each independently represent an alkyl chain having 1 or more carbon atoms and 3 or less carbon atoms, and Xn is hydrogen, a hydroxyl group, an alkyl group having 1 or more carbon atoms and 6 or less carbon atoms, and 1 or more carbon atoms. It represents an alkylol group of 3 or less, or an allylalkoxyalkyl group represented by the formula (2). M represents an integer of 1 to 3, and n represents an integer satisfying m + n = 4. In the formula (2). , R ³ and R ⁴ each independently represent an alkyl chain having 1 to 3 carbon atoms.)

Since the compound represented by the formula (1) contains many double bonds in the molecule, it has high reactivity, oxidative polymerization of the ink is promoted, curing of the ink is promoted, and the oily medium contained in the ink is used. It is fixed in the recording medium. As a result, it is possible to provide an oil-based recording liquid having improved storage stability in a clear folder.

The "alkyl chain having 1 or more and 3 or less carbon atoms" in R ¹ and R ² can be a linear or branched alkyl group, for example, a methyl chain, an ethyl chain, an n-propyl chain, or an isopropyl chain. Can be mentioned. The "alkyl group having 1 or more and 6 or less carbon atoms" in Xn can be a linear or branched alkyl group, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or n. -Butyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, n-hexyl group, isohexyl group, sec-hexyl group and the like can be mentioned. Examples of the "alkyrole group having 1 or more and 3 or less carbon atoms" include a methylol group, an ethylol group, and a propyrrole group.

As the allyl compound, among the compounds represented by the above formula (1), the compounds represented by the following formulas (4) to (6) are preferable.

The compound represented by the above formula (4) (SP value 12.6, iodine value 297), the compound represented by the above formula (5) (SP value 11.5, iodine value 231), the above formula (6). As commercially available products of the represented compounds (SP value 8.5, iodine value 343), for example, Neoallyl P-30, Neoallyl T-20, and Neoallyl P-40 (all manufactured by Osaka Soda Co., Ltd.) should be used. You can also.

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

The allyl compound is preferably the main component of the oil-based medium, and is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 60% by mass or more, based on the total mass of the oil-based inkjet ink composition. It is 80% by mass or more.

1.2.3. Second Organic Solvent In the oil-based inkjet ink composition according to the present embodiment, the content of the second organic solvent having an SP value of 9.0 or less and an iodine value of 100 or less is 30% by mass or less as an oil-based medium. Is preferable.

The second organic solvent may impair the storage property of the clear folder, and since the number of double bonds is small, it takes time to oxidatively polymerize the ink. Therefore, it is preferably not contained in the ink according to the present embodiment, and even if it is contained, it is preferably 30% by mass or less, more preferably 20% by mass or less, and 10% by mass or less. Is more preferable.

As an oil-based medium, the content of an organic solvent having an SP value of more than 9.0 and less than 9.5 and an iodine value of more than 100 and less than 120 is 50% by mass or less. It is preferably 30% by mass or less, and more preferably 30% by mass or less.

1.2.4. Drying Oil The oil-based inkjet ink composition according to the present embodiment preferably contains a drying oil. Since drying oil has a high viscosity, if it is used in a large amount as an ink for inkjet recording, a problem will occur in ejection property. However, PP, which is a material of a clear folder, has a low attack property and has many double bonds. Oxidative polymerization is promoted. Therefore, by using it as an auxiliary in the ink 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. As a result, even if the recorded material is sandwiched between the clear folders, it is possible to provide an oil-based recording liquid in which the residual solvent is suppressed from being transferred to the clear folder and the storage property of the recorded material in the clear folder is improved.

Here, the dry oil refers to an oil having an iodine value of 130 or more, and examples thereof include flaxseed oil, tung oil, mustard oil, shiso oil, walnut oil, mustard oil, red flower oil, and sunflower oil. These drying oils can be used alone or in admixture 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 ejection property.

1.2.5. Other Oil-based Ink Compositions of the oil-based inkjet ink composition according to the present embodiment further contain various known vegetable oils and / or petroleum-based solvents other than the above-mentioned first allyl compound, second solvent and drying oil as the oil-based medium. It is possible to use both non-polar organic solvents and polar organic solvents.

1.2.5.1. 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 hydrocarbon solvents such as naphthen-based, paraffin-based, and isoparaffin-based, fluorine-based surfactants, and silicon-based interfaces. Activators and the like can be mentioned. As these non-polar organic solvents, commercially available ones may be used, for example, aliphatic saturated hydrocarbons such as dodecane, Isopar manufactured by Exxon Mobile Co., Ltd., Exol, AF solvent manufactured by JX Nikko Nisseki Energy Co., Ltd. , Normal Paraffin H, AS Sol manufactured by Wilvey Co., Ltd., Dust Clean manufactured by Matsumura Petroleum Co., Ltd., Sansen manufactured by Sun Petroleum Co., Ltd., Samper, Surflon manufactured by AGC Seimi Chemical Co., Ltd. and the like.

1.25.2. 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-based 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 or more and 32 or less 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, isooctyl stearate, isopropyl isostearate, 2 pivalic acid -Examples include octyldodecyl, diisopropyl adipate, diisopropyl sebacate, diethyl sebacate, propylene glycol monocaprylate, trimethyl propane tri2-ethylhexanoate, and glyceryl tri2-ethylhexanoate. Further, soybean oil fatty acid methyl, soybean oil fatty acid isobutyl, tall oil fatty acid methyl, tall oil fatty acid isobutyl and the like, which are esters of dry oil fatty acid and alcohol, can also be used.

Examples of the alcohol-based solvent include aliphatic higher alcohols having 12 or more carbon atoms in one molecule, and examples thereof include higher alcohols such as isomiristyl 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-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. Acids, oleic acid, isostearic acid and the like can be mentioned.

Examples of the ether-based solvent include glycol ethers such as diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, and propylene glycol dibutyl ether, as well as the acetate of glycol ethers.

The content of these other oil-based 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.

1.3. 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 complex. In the oil-based inkjet ink composition according to the present embodiment, the metal soap or the metal complex is also called a dryer (curing accelerator) and acts as an oxidizing agent that promotes oxidative polymerization of the organic compound contained in the oil-based 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. Ink. As a result, even if the recorded material is sandwiched between the clear folders, the oil-based medium is suppressed from being transferred to the clear folder, and the deformation of the clear folder is prevented.

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 can be 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, organic acids such as propionic acid, octyl acid, naphthenic acid, neodecanoic acid, tung oil acid, flaxseed oil acid, soybean oil acid, and resin acid can be used, but they have an excellent effect of promoting drying. From the point of view, it is preferable to use an aliphatic monocarboxylic acid having 3 to 12 carbon atoms, and more preferably to use octyl acid, naphthenic acid and neodecanoic acid. These may be used alone or in combination of two or more.

Among these metal-containing compounds (metal salts), for example, cobalt and the like promote oxidation at the interface between the ink coating film and air, and other manganese and the like are moderate and act on the inside as well as surface oxidation. Promotes overall polymerization. Auxiliary dryers such as zirconium and calcium improve overall performance in combination with the dryers mentioned above, but have little effect on their own.

As the organic acid metal salt used in this embodiment, for example, the 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 the three Rs in the molecule may be the same or different.)
Examples thereof include organic acid metal salts represented by.

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

As described above, in the present embodiment, examples of the metal soap and the metal complex include a cobalt dryer and a manganese dryer, but it is preferable to use a manganese dryer from the viewpoint of the usage environment. 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. The ligand can be used alone or in combination of two or more.

As the manganese dryer, manganese neodecanoate is preferably used, and examples of commercially available products include DICNATE Mn 6.5% SB manufactured by DIC Corporation.

Examples of the organic acid metal salt used as another dryer include an organic acid cobalt boron metal salt and an organic acid manganese boron metal salt. These may be used alone or in combination, but when they are used in combination, they are excellent in drying property of the coating film on a thick film, which is considered to be difficult to uniformly cure, so that they are preferably used in combination. Further, 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 metal salt, the drying property of the coating film on a thick film is also excellent, so that the combined use is preferable. Further, when the organic acid cobalt boron metal salt and the organic acid manganese metal salt are used in combination, a low-priced dryer having an excellent drying promoting 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 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 ease of handling and uniform mixing. The diluted organic solvent is not limited as long as it can uniformly dissolve the above organic acid metal salt and is inactive with respect to the organic acid metal salt. For example, toluene, xylene, heptane, hexane, cyclohexane, etc. 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, methyl carbitol, Ether-based solvents such as butyl carbitol can be used, and these may be used alone or in combination of two or more.

1.4. Other Ingredients Other additives contained in a normal oil-based inkjet ink composition may be further added to the oil-based inkjet ink composition according to the present embodiment. 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.

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 fibers such as acrylic resin, styrene acrylic resin, rosin-modified resin, phenol resin, terpene resin, polyester resin, polyamide resin, epoxy resin, vinyl chloride acetic acid, vinyl copolymer resin, and cellulose acetate butyrate. Examples thereof include based resins and vinyl toluene-α-methylstyrene copolymer resins. These binder resins may be used alone or in combination of two or more.

1.5. Method for Producing Oil-Based 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, a pigment, a dispersant, and an organic solvent (a part) are first mixed, and then a pigment dispersion is prepared by a ball mill, a bead mill, an ultrasonic wave, a jet mill, or the like, and a desired pigment dispersion is prepared. 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 under stirring to obtain an oil-based inkjet ink composition.

1.6. Physical Properties The oil-based inkjet ink composition according to this embodiment preferably has a surface tension of 20 mN / m or more and 50 mN / m at 20 ° C. from the viewpoint of a 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 checking the surface tension when the platinum plate is wet with ink in an environment of 20 ° C. using an automatic surface tension meter CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.). be able to.

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

1.7. Applications The oil-based inkjet ink composition according to the present embodiment is contained in an ink cartridge of a known inkjet recording device, droplets of ink are ejected, and the droplets are adhered to a recording medium such as paper to record an image. .. As the inkjet recording device, an inkjet recording device that is equipped with an electrostraining element capable of vibrating based on an electric signal and is configured to be able to eject ink by the vibration of the electrostraining element is preferable. The oil-based inkjet ink composition according to the present embodiment contains 50% by mass or more of a first organic solvent having an SP value of 9.5 or more and an iodine value of 120 or more as an oil-based medium. Since the oil-based medium contains the allyl compound, there is no problem in ejecting ink, and an image can be recorded. Further, in the recorded material obtained by using the oil-based inkjet ink composition according to the present embodiment, deformation of the clear folder is suppressed due to the influence of the residual solvent in the obtained image.

As shown above, according to the oil-based inkjet ink composition according to the present embodiment, the content of the first organic solvent in which the oil-based medium has an SP value of 9.5 or more and an iodine value of 120 or more is 50. It is possible to provide an oil-based recording liquid capable of suppressing deformation of the clear folder due to printed matter using this ink for a long period of time when the mass% or more or the oil-based medium contains an allyl compound. it can.

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

2.1. Preparation of oil-based ink composition In Examples 1 to 13 and Comparative Example 1, each material was mixed and stirred so as to have the composition (mass%) shown in Table 1 below, and after being completely dissolved, a membrane filter having a pore size of 1 μm was obtained. Each oil-based ink composition was obtained by filtering with. Then, the following clear folder deformation evaluation test was carried out for each oil-based ink composition.

In Example 14, a solvent of 1: 5000 g, linseed oil: 500 g, a pigment of 1: 500 g, and a dispersant: 300 g were placed in a 10 L stainless steel container and stirred with a dissolver manufactured by Inoue Seisakusho for 1 hour to produce a mill base. The mill base was subjected to 5-pass dispersion treatment by pass operation using Star Mill LMZ (peripheral speed 12 m / s, beads used: zirconia φ0.1 mm, bead filling rate: 85%) manufactured by Ashizawa Finetech Co., Ltd. Then, it was centrifuged with a Hitachi Koki cooling centrifuge (CR7N) at an acceleration of 11000 G for 20 minutes, and then filtered through a 3 μm filter. 3600 g of Solvent 1 was added to the filtrate, and the mixture was sufficiently stirred to obtain the oil-based ink composition of Example 14.

In Example 15, in the method for producing an oil-based ink of Example 14, pigment 1 was changed to pigment 2, and the ink of Example 15 was produced in the same manner under other conditions.

In Example 16, in the method for producing an oil-based ink of Example 14, the solvent 1 was changed to the solvent 3, and the ink of Example 16 was produced in the same manner under other conditions.

In Example 17, in the method for producing an oil-based ink of Example 14, the solvent 1 was changed to the solvent 3, the pigment 1 was changed to the pigment 2, and the ink of Example 16 was produced in the same manner under other conditions.

The materials described in Table 1 other than the compound names are as follows.
-Solvent 1: Allyl ether A (SP value: 12.6, iodine value: 297)
: Neoallyl (registered trademark) P-30 manufactured by Osaka Soda Co., Ltd.
-Solvent 2: Allyl ether B (SP value: 11.5, iodine value: 231)
: Neoallyl (registered trademark) T-20 manufactured by Osaka Soda Co., Ltd.
-Solvent 3: Linseed oil fatty acid 2-ethylhexyl
2-Ethylhexyl linolenic acid (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%
-Solvent 4: Linseed oil fatty acid methyl ester
Methyl linolenic acid (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%
-Solvent 5: Methyl oleate: manufactured by Toei Chemical Co., Ltd., TOENOL # 2180
SP value: 8.6, iodine value: 94
-Drying oil: Kaneda Co., Ltd., flaxseed oil-Mn soap: DIC Corporation, DICDATE Mn 6.5% SB
-Oil-soluble dye: BASF, Neozapon Blue 807
-Pigment 1: Cinquasia Magenta D4550J (manufactured by BASF)
-Pigment 2: Heliogen Blue D7088 (manufactured by BASF)
Dispersant: Solspece 13940

In Examples 18 to 29 and Comparative Examples 2 to 5, each material was mixed and stirred to completely dissolve the materials so as to have the composition (mass%) shown in Table 2 below, and then filtered through a membrane filter having a pore size of 1 μm. , Each oil-based ink composition was obtained. Then, the following clear folder deformation evaluation test was carried out for each oil-based ink composition.

In Example 24, allyl ether A: 5000 g, linseed oil: 800 g, pigment 1: 500 g, and dispersant: 300 g were placed in a 10 L stainless steel container and stirred with a dissolver manufactured by Inoue Seisakusho for 1 hour to produce a mill base. The mill base was subjected to 5-pass dispersion treatment by pass operation using Star Mill LMZ (peripheral speed 12 m / s, beads used: zirconia φ0.1 mm, bead filling rate: 85%) manufactured by Ashizawa Finetech Co., Ltd. Then, it was centrifuged with a Hitachi Koki cooling centrifuge (CR7N) at an acceleration of 11000 G for 20 minutes, and then filtered through a 3 μm filter. 3300 g of allyl ether A was added to the filtrate, and the mixture was sufficiently stirred to obtain the oil-based ink composition of Example 7.

In Example 25, in the method for producing the oil-based ink of Example 24, the pigment 1 was changed to the pigment 2, and the ink of Example 24 was produced in the same manner under other conditions.

In Example 26, in the method for producing an oil-based ink of Example 24, allyl ether A was changed to allyl ether B, and the ink of Example 26 was produced in the same manner under other conditions.

In Example 27, in the method for producing an oil-based ink of Example 24, allyl ether A was changed to allyl ether B, pigment 1 was changed to pigment 2, and the ink of Example 27 was produced in the same manner under other conditions. did.

In Example 28, in the method for producing an oil-based ink of Example 24, all of the allyl ether A and linseed oil were changed to allyl ether C, and the ink of Example 28 was produced in the same manner under other conditions.

In Example 29, in the method for producing an oil-based ink of Example 24, the allyl ether A was changed to allyl ether C, and the ink of Example 29 was produced in the same manner under other conditions.

In Table 2, the materials other than the compound names are as follows.
-Allyl ether A: Neoallyl (registered trademark) P-30 manufactured by Osaka Soda Co., Ltd.
-Allyl ether B: Neoallyl (registered trademark) T-20 manufactured by Osaka Soda Co., Ltd.
-Allyl ether C: Neoallyl (registered trademark) P-40 manufactured by Osaka Soda Co., Ltd.
-Methyl oleate: manufactured by Toei Chemical Co., Ltd., TOENOL # 2180
・ Linseed oil: Kaneda Co., Ltd. ・ Tung oil: Kaneda Co., Ltd. ・ Mn soap: DIC Corporation, DICNAME Mn 6.5% SB
-Oil dye: BASF, Neozapon Blue 807
-Pigment 1: Cinquasia Magenta D4550J (manufactured by BASF)
-Pigment 2: Heliogen Blue D7088 (manufactured by BASF)
Dispersant: Solspece 13940

2.2. Clear folder deformation evaluation test Each oil-based ink composition obtained was filled into the ink cartridge of a modified machine of the inkjet printer PX-M7050F (manufactured by Seiko Epson Corporation), and solid printed on double-sided high-quality plain paper (manufactured by Seiko Epson Corporation) A rectangular shape (20 cm × 28 cn) was applied, and the printed matter was inserted into a clear folder made of PP. The clear folder in which the printed matter was inserted was placed at 23 ° C./50% R. H. It was left to stand horizontally for 30 days in the environment. Then, the amount of the clear folder that had been allowed to bend outward 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 of the obtained oil-based recording liquid compositions was filled into the ink cartridge of a modified machine of an inkjet printer PX-M7050F (manufactured by Seiko Epson Corporation), and a test pattern including characters and 1-dot ruled lines (vertical, horizontal) was included. (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 evaluation results of Examples 1 to 13 and Comparative Example 1 are shown in the bottom row of Table 1. In Examples 1 to 13 in which the SP value was 9.5 or more and the content of the organic solvent having an iodine value of 120 or more was 50% by mass or more, the amount of deformation was small. In particular, in Examples 5 to 8 further containing drying oil and Examples 9 to 12 containing both drying oil and Mn soap, the amount of deformation was suppressed to less than 10 mm, and the clear folder storage property was improved. In Example 13 in which the SP value is 9.0 or less and the content of the organic solvent having an iodine value of 100 or less is 30% by mass or more, the amount of deformation is large even if both the drying oil and the Mn soap are contained. There was no problem in using it. Further, the same effect was observed in Examples 14 to 17 containing the drying oil and the dispersant. On the other hand, the content of the organic solvent having an SP value of 9.5 or more and an iodine value of 120 or more is 50% by mass or less, the SP value is 9.0 or less, and the iodine value is 100 or less. In Comparative Example 1 in which the solvent content was 30% by mass or more, both the drying oil and the Mn soap were contained, but the amount of deformation was large and the clear folder storage property was inferior.

As shown above, the oil-based recording liquid has a SP value of 9.5 or more and an iodine value of 120 or more, and the content of the organic solvent is 50% by mass or more, so that the clear folder is dramatically deformed. It is possible to provide an oil-based recording liquid that can be suppressed, and by further adding Mn soap or a drying oil, it is possible to suppress deformation of the clear folder due to printed matter using an oil-based ink for a long period of time. I understood.

The evaluation results of Examples 18 to 29 and Comparative Examples 2 to 5 are shown in the bottom row of Table 2. Examples 18, 19 and 28 containing the allyl compound had a smaller amount of deformation as compared with Comparative Example 2 containing no allyl compound. Further, in Examples 20 and 21 containing Mn soap in addition to the allyl compound, the amount of deformation was further reduced, and in Examples 22 and 23 in which both Mn soap and drying oil were added, the amount of deformation was suppressed to less than 10 mm. , Clear folder storage was improved. Further, the same effect was observed in Examples 24 to 27 and 29 containing the drying oil and the dispersant. On the other hand, in the comparative example not containing the allyl compound, the amount of deformation was large even when Mn soap and drying oil were added, and the clear folder storage property was inferior.

As shown above, by containing the allyl compound in the oil-based recording liquid, the deformation of the clear folder can be dramatically suppressed, and by further adding Mn soap or drying oil, the recorded material using the oil-based ink is used. It was found that it is possible to provide an oil-based recording liquid capable of suppressing the deformation of the clear folder due to the above for a long period of time.

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

Claims (5)

Including coloring material and oil-based medium,
The oily medium is a drying oil containing an allyl compound having an SP value of 9.5 or more and an iodine value of 120 or more, and an unsaturated fatty acid having an SP value of 9.5 or more and an iodine value of 120 or more. A first organic solvent that is one or more selected from the esters of fatty acids and alcohols ,
Contains drying oil ,
The content of the first organic solvent Ri der least 50 wt%,
An oil- based recording liquid having a drying oil content of 0.05% by mass or more and 10% by mass or less . The oil-based recording solution according to claim 1, wherein the content of the second organic solvent having an SP value of 9.0 or less and an iodine value of 100 or less is 30% by mass or less. The oil-based recording solution according to claim 1 or 2 , further comprising an organic acid metal salt represented by the following 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 the three Rs in the molecule may be the same or different.) The oil-based recording solution according to any one of claims 1 to 3, wherein the allyl compound is a compound represented by the following formula (1).

(In the formula (1), R ¹ and R ² each independently represent an alkyl chain having 1 or more carbon atoms and 3 or less carbon atoms, and Xn is hydrogen, a hydroxyl group, an alkyl group having 1 or more carbon atoms and 6 or less carbon atoms, and 1 or more carbon atoms. It represents an alkylol group of 3 or less, or an allylalkoxyalkyl group represented by the formula (2). M represents an integer of 1 to 3, and n represents an integer satisfying m + n = 4. In the formula (2). , R ³ and R ⁴ each independently represent an alkyl chain having 1 to 3 carbon atoms.) The oil-based recording solution according to any one of claims 1 to 4 , wherein the oil-based recording solution is for inkjet recording.